Ethylene interpolymer products and films

ABSTRACT

This disclosure relates to ethylene interpolymer compositions and films prepared therefrom. Specifically: ethylene interpolymer products having: a dimensionless nonlinear rheology network parameter, Δ int. , greater than or equal to 0.01, satisfying 0.01×(Z−50) 0.78 ≤Δ int. ≤0.01×(Z−60) 0.78  inequality wherein Z is a normalized molecular weight defined by 
             Z   =       M   w       M   e             
where M w  and M e  are the weight average and entanglement molecular weights, and; a residual catalytic metal of from ≥0.03 to ≤5 ppm of hafnium. The disclosed ethylene interpolymer products have a melt index from about 0.3 to about 500 dg/minute, a density from about 0.855 to about 0.975 g/cc, a polydispersity,
 
                 M   w       M   n       ,         
from about 1.7 to about 25 and a Composition Distribution Breadth Index (CDBI 50 ) from about 1% to about 98%.

CROSS REFERENCE TO RELATED PATENT APPLICATION

This application is a Divisional of Ser. No. 16/826,689, filed Mar. 23,2020, which is a Continuation-In-Part of U.S. Ser. No. 15/805,268, whichwas filed Nov. 7, 2017, entitled “Interpolymer Products and Film”, bothof which are herein incorporated by reference in their entirety.

BACKGROUND

Solution polymerization processes are typically carried out attemperatures that are above the melting point of the ethylenehomopolymer or copolymer produced. In a typical solution polymerizationprocess, catalyst components, solvent, monomers and hydrogen are fedunder pressure to one or more reactors.

For ethylene polymerization, or ethylene copolymerization, reactortemperatures can range from 80° C. to 300° C. while pressures generallyrange from 3 MPag to 45 MPag. The ethylene homopolymer or copolymerproduced remains dissolved in the solvent under reactor conditions. Theresidence time of the solvent in the reactor is relatively short, forexample, from 1 second to 20 minutes. The solution process can beoperated under a wide range of process conditions that allow theproduction of a wide variety of ethylene polymers. Post reactor, thepolymerization reaction is quenched to prevent further polymerization,by adding a catalyst deactivator. Optionally, the deactivated solutionmay be passivated by adding an acid scavenger. The deactivated solution,or optionally the passivated solution, is then forwarded to polymerrecovery where the ethylene homopolymer or copolymer is separated fromprocess solvent, unreacted residual ethylene and unreacted optionalα-olefin(s).

In solution polymerization there is a need for improved processes thatproduce ethylene interpolymers at higher production rates, i.e. thepounds of ethylene interpolymer produced per hour is increased. Higherproduction rates increase the profitability of the solutionpolymerization plant. The catalyst formulations and solutionpolymerization processes disclosed herein satisfy this need.

In solution polymerization there is also a need to increase themolecular weight of the ethylene interpolymer produced at a givenreactor temperature. Given a specific catalyst formulation, it is wellknown to those of ordinary experience that polymer molecular weightincreases as reactor temperature decreases. However, decreasing reactortemperature can be problematic when the viscosity of the solutionbecomes too high. As a result, in solution polymerization there is aneed for catalyst formulations that produce high molecular weightethylene interpolymers at high reactor temperatures (or lower reactorviscosities). The catalyst formulations and solution polymerizationprocesses disclosed herein satisfy this need.

In the solution polymerization process, 3333 there is also a need forcatalyst formulations that are very efficient at incorporating one ormore α-olefins into a propagating macromolecular chain. In other words,at a given [α-olefin/ethylene] weight ratio in a solution polymerizationreactor, there is a need for catalyst formulations that produce lowerdensity ethylene/α-olefin copolymers. Expressed alternatively, there isa need for catalyst formulations that produce an ethylene/α-olefincopolymer, having a specific density, at a lower [α-olefin/ethylene]weight ratio in the reactor feed. Such catalyst formulations efficientlyutilize the available α-olefin and reduce the amount of α-olefin insolution process recycle streams.

The catalyst formulations and solution process disclosed herein, produceunique ethylene interpolymer products that have desirable properties ina variety of end-use applications. One non-limiting end-use applicationincludes packaging films containing the disclosed ethylene interpolymerproducts. Non-limiting examples of desirable film properties includeimproved optical properties, lower seal initiation temperature andimproved hot tack performance. Films prepared from the ethyleneinterpolymer products, disclosed herein, have improved properties.

SUMMARY OF DISCLOSURE

One embodiment of this disclosure is an ethylene interpolymer productcomprising at least one ethylene interpolymer, where the ethyleneinterpolymer product has: a dimensionless nonlinear rheology networkparameter, Δ_(int.), greater than or equal to 0.01 and satisfying theinequality [0.01×(Z−50)^(0.78)≤Δ_(int.)≤0.01×(Z−60)^(0.78)] wherein Z isa normalized molecular weight defined by

$Z = \frac{M_{w}}{M_{e}}$where M_(w) and M_(e) are the SEC weight average molecular weight andmolecular weight between entanglements of said ethylene interpolymer,respectively; and a residual catalytic metal of from ≥0.03 to ≤5 ppm ofhafnium. The ethylene interpolymer product may have a melt index (I₂)from 0.3 to 500 dg/minute, a density from 0.855 to 0.975 g/cc and from 0to 25 mole percent of one or more α-olefins. Suitable α-olefins includeone or more C₃ to C₁₀ α-olefins. Embodiments of the ethyleneinterpolymer product have a polydispersity,

$\frac{M_{w}}{M_{n}},$from 1.7 to 25, where M_(w) and M_(n) are the weight and number averagemolecular weights, respectively, as determined by conventional sizeexclusion chromatography (SEC). Embodiments of ethylene interpolymerproducts have a CDBI₅₀ from 1% to 98%, where CDBI₅₀ is measured usingCTREF.

Disclosed herein is the manufacture of said ethylene interpolymerproducts using a continuous solution polymerization process employing atleast one homogeneous catalyst formulation. One embodiment of a suitablehomogeneous catalyst formulation is a bridged metallocene catalystformulation comprising a component A defined by Formula (I)

where M is a metal selected from titanium, hafnium and zirconium; G isthe element carbon, silicon, germanium, tin or lead; X represents ahalogen atom, R₆ groups are independently selected from a hydrogen atom,a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryloxide radical, these radicals may be linear, branched or cyclic orfurther substituted with halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀alkoxy radicals, C₆₋₁₀ aryl or aryloxy radicals; R₁ represents ahydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, aC₆₋₁₀ aryl oxide radical or alkylsilyl radicals containing at least onesilicon atom and C₃₋₃₀ carbon atoms; R₂ and R₃ are independentlyselected from a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀alkoxy radical, a C₆₋₁₀ aryl oxide radical or alkylsilyl radicalscontaining at least one silicon atom and C₃₋₃₀ carbon atoms, and; R₄ andR₅ are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical a C₆₋₁₀ aryl oxide radical, oralkylsilyl radicals containing at least one silicon atom and C₃₋₃₀carbon atoms.

Disclosed herein is an improved continuous solution polymerizationprocess where the improved process comprises: polymerizing ethylene andoptionally at least one α-olefin, in a process solvent, in one or morereactors using a bridged metallocene catalyst to form the ethyleneinterpolymer product; where the improved process has an increasedproduction rate, PR^(I), defined by the following formula;

${PR}^{I} = {{100 \times \frac{{PR^{A}} - {PR^{C}}}{PR^{C}}} \geq {10\%}}$

where PR^(A) is the production rate of the improved process and PR^(C)is a comparative production rate of a comparative continuous solutionpolymerization process where the bridged metallocene catalystformulation has been replaced with an unbridged single site catalystformulation.

Additional embodiments include a bridged metallocene catalystformulation comprising: an alumoxane co-catalyst (component M); a boronionic activator (component B), and, optionally, a hindered phenol(component P). Non-limiting examples of components M, B and P include:methylalumoxane (MMAO-7), trityl tetrakis (pentafluoro-phenyl) borateand 2,6-di-tert-butyl-4-ethylphenol, respectively.

The improved process employing further comprises: a process solventcomprising one or more C₅ to C₁₂ alkanes and one or more reactorsoperating at temperatures from 80° C. to 300° C. and pressures from 3MPag to 45 MPag. Embodiments may include reactor conditions such thatthe process solvent in one or more reactors has an average reactorresidence time from 10 seconds to 720 seconds. Further embodiments mayinclude reactor conditions such that the catalyst inlet temperatureemployed in one or more reactors may vary from 20° C. to 180° C.

Other embodiments include an improved continuous solution polymerizationprocess where an ethylene interpolymer product is formed by polymerizingethylene, and optionally at least one α-olefin, in a process solvent, inone or more reactors, using a bridged metallocene catalyst formulationand the improved process is characterized by (a) and/or (b):

(a) the ethylene interpolymer product has at least a 10% improved(higher) weight average molecular weight, M_(w), as defined by thefollowing formula

${\%{Improved}M_{w}} = {{100 \times \frac{\left( {M_{w}^{A} - M_{w}^{C}} \right)}{M_{w}^{C}}} \geq {10\%}}$

where M_(w) ^(A) is a weight average molecular weight of the ethyleneinterpolymer product produced using the improved process and M_(w) ^(C)is a comparative weight average molecular weight of a comparativeethylene interpolymer product; where the comparative ethyleneinterpolymer product is produced in a comparative process by replacingthe bridged metallocene catalyst formulation with an unbridged singlesite catalyst formulation;

(b) an [α-olefin/ethylene] weight ratio, employed in the improvedprocess, is reduced (improved) by at least 70% as defined by thefollowing formula

$\%{Reduced}{\left\lbrack \frac{\alpha - {olefin}}{ethylene} \right\rbrack = {{100 \times \left\{ \frac{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}} \right\}} \leq {{- 7}0\%}}}$

where

$\left( \frac{\alpha - {olefin}}{ethylene} \right)^{A}$represents the weight of the α-olefin added to the improved processdivided by the weight of ethylene added to the improved process, wherethe ethylene interpolymer product having a target density is produced bya bridged metallocene catalyst formulation, and;

$\left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}$represents a comparative weight ratio required to produce a comparativee ylene interpolymer product having the target density, where thecomparative ethylene interpolymer product is synthesized in acomparative process by replacing the bridged metallocene catalystformulation with an unbridged single site catalyst formulation.

Embodiments of the ethylene interpolymer product may comprise a firstethylene interpolymer. Other embodiments of the ethylene interpolymerproduct may comprise a first ethylene interpolymer and a third ethyleneinterpolymer. Other embodiments of the ethylene interpolymer product maycomprise a first ethylene interpolymer and a second ethyleneinterpolymer. Other embodiments of the ethylene interpolymer product maycomprise a first ethylene interpolymer, a second ethylene interpolymerand a third ethylene interpolymer.

The first ethylene interpolymer has a melt index from 0.01 to 200dg/minute and a density from 0.855 g/cc to 0.975 g/cc; the firstethylene interpolymer may comprise for 5 to 100 wt. % of the ethyleneinterpolymer product. The second ethylene interpolymer may comprise from0 to 95 wt. % of the ethylene interpolymer product, has melt index from0.3 to 1000 dg/minute and a density from 0.855 g/cc to 0.975 g/cc. Thethird ethylene interpolymer may comprise from 0 to 30 wt. % of theethylene interpolymer product, has a melt index from 0.4 to 2000dg/minute and a density from 0.855 g/cc to 0.975 g/cc. Weight percent,wt. %, is the weight of the first, the second or the optional thirdethylene interpolymer, individually, divided by the total weight of theethylene interpolymer product, melt index is measured according to ASTMD1238 (2.16 kg load and 190° C.) and density is measured according toASTM D792.

In further embodiments, the upper limit on the CDBI₅₀ of the first andsecond ethylene interpolymers may be 98%, in other cases 95% and instill other cases 90%; and the lower limit on the CDBI₅₀ of the firstand second ethylene interpolymers may be 70%, in other cases 75% and instill other cases 80%. The upper limit on the CDBI₅₀ of the thirdethylene interpolymer may be 98%, in other cases 95% and in still othercases 90%; and the lower limit on the CDBI₅₀ of the third ethyleneinterpolymer may be 35%, in other cases 40% and in still other cases45%.

In other embodiments, the upper limit on the

$\frac{M_{w}}{M_{n}}$of the first and second ethylene interpolymers may be 2.4, in othercases 2.3 and in still other cases 2.2; and the lower limit on theM_(w)/M_(n) the first and second ethylene interpolymers may be 1.7, inother cases 1.8 and in still other cases 1.9. The upper limit on theM_(w)/M_(n) of the third ethylene interpolymer may be 5.0, in othercases 4.8 and in still other cases 4.5; and the lower limit on the

$\frac{M_{w}}{M_{n}}$of the optional third ethylene interpolymer may be 1.7, in other cases1.8 and in still other cases 1.9.

In this disclosure the amount of long chain branching in ethyleneinterpolymers was characterized by the dimensionless nonlinear rheologynetwork parameter ‘Δ_(int.)’. In some embodiments the upper limit on theΔ_(int.) of the first and second ethylene interpolymers may be 0.09, inother cases 0.07 and in still other cases 0.05 (dimensionless); and thelower limit on the Δ_(int.) of the first and second ethyleneinterpolymers is greater than or equal to 0.01 (dimensionless). Theupper limit on the Δ_(int.) of the third ethylene interpolymer may be0.09, in other cases 0.07 and in still other cases 0.05 (dimensionless);and the lower limit on the Δ_(int.) of the third ethylene interpolymersmay be greater than or equal to 0.01, in other cases greater than 0.015,and in still other cases greater than 0.02 (dimensionless).

In this disclosure, the Unsaturation Ratio ‘UR’ was used to characterizethe degree of unsaturation in ethylene interpolymers. In someembodiments the upper limit on the UR of the first and second ethyleneinterpolymers may be 0.06, in other cases 0.04 and in still other cases0.02 (dimensionless), and the lower limit on the UR of the first andsecond ethylene interpolymers may be −0.40, in other cases −0.30 and instill other cases −0.20 (dimensionless). The upper limit on the UR ofthe third ethylene interpolymer may be 0.06, in other cases 0.04 and instill other cases 0.02 (dimensionless); and the lower limit on UR of thethird ethylene interpolymer may be −1.0, in other cases −0.95 and instill other cases −0.9.

In this disclosure the amount of residual catalytic metal in ethyleneinterpolymers was characterized by Neutron Activation Analysis ‘NAA’.The upper limit on the ppm of metal A^(R1) in the first ethyleneinterpolymer may be 5.0 ppm, in other cases 4.0 ppm and in still othercases 3.0 ppm, and the lower limit on the ppm of metal A^(R1) in thefirst ethylene interpolymer may be 0.03 ppm, in other cases 0.09 ppm andin still other cases 0.15 ppm. The upper limit on the ppm of metalA^(R2) in the second ethylene interpolymer may be 5.0 ppm, in othercases 4.0 ppm and in still other cases 3.0 ppm; while the lower limit onthe ppm of metal A^(R2) in the second ethylene interpolymer may be 0.03ppm, in other cases 0.09 ppm and in still other cases 0.15 ppm. Thecatalyst residue in the third ethylene interpolymer reflected thecatalyst employed in its manufacture. If a bridged metallocene catalystformulation was used, the upper limit on the ppm of metal A^(R3) in thethird ethylene interpolymer may be 5.0 ppm, in other cases 4.0 ppm andin still other cases 3.0 ppm; and the lower limit on the ppm of metalA^(R3) in the third ethylene interpolymer may be 0.03 ppm, in othercases 0.09 ppm and in still other cases 0.15 ppm. If an unbridged singlesite catalyst formulation was used, the upper limit on the ppm of metalC^(R3) in the third ethylene interpolymer may be 3.0 ppm, in other cases2.0 ppm and in still other cases 1.5 ppm and the lower limit on the ppmof metal C^(R3) in the third ethylene interpolymer may be 0.03 ppm, inother cases 0.09 ppm and in still other cases 0.15 ppm. In the case of ahomogeneous catalyst formulation containing a bulky ligand-metal complexthat is not a member of the genera defined by Formula (I) or (II), theupper limit on the ppm of metal B^(R3) in the third ethyleneinterpolymer may be 5.0 ppm, in other cases 4.0 ppm and in still othercases 3.0 ppm; and the lower limit on the ppm of metal B^(R3) in thethird ethylene interpolymer may be 0.03 ppm, in other cases 0.09 ppm andin still other cases 0.15 ppm. If a heterogeneous catalyst formulationwas used, the upper limit on the ppm of metal Z^(R3) in the thirdethylene interpolymer may be 12 ppm, in other cases 10 ppm and in stillother cases 8 ppm; and the lower limit on the ppm of metal Z^(R3) in thethird ethylene interpolymer may be 0.5 ppm, in other cases 1 ppm and instill other cases 3 ppm.

Non-limiting embodiments of manufactured articles include a filmcomprising at least one layer, where the layer comprises at least one ofthe ethylene interpolymer products disclosed herein; where the ethyleneinterpolymer product has 1) a dimensionless nonlinear rheologyintegrated network parameter, Δ_(int.), greater than or equal to 0.01and satisfying the inequality[0.01×(Z−50)^(0.78)≤Δ_(int.)≤0.01×(Z−60)^(0.78)] wherein Z is anormalized molecular weight defined by

$Z = \frac{M_{w}}{M_{e}}$where M_(w) and M_(e) are the weight average and entanglement molecularweights and 2) a residual catalytic metal of from ≤0.03 to ≥5 ppm ofhafnium. In other embodiments the film has a film gloss at 45° that isfrom 10% to 30% higher relative to a comparative film and/or the filmhas a film haze that is from 30% to 50% lower compared to a comparativefilm; where the comparative film has the same composition except theethylene interpolymer product synthesized with a bridged metallocenecatalyst formulation is replaced with a comparative ethyleneinterpolymer product synthesized with an unbridged single site catalystformulation.

Additional film embodiments include films where the at least one layerfurther comprises at least one second polymer; where the second polymermay be one or more ethylene polymers, one or more propylene polymers ora mixture of ethylene polymers and propylene polymers. Furtherembodiments include films having a total thickness from 0.5 mil to 10mil. Other embodiments include multilayer films that have from 2 to 11layers, where at least one layer comprises at least one ethyleneinterpolymer product.

BRIEF DESCRIPTION OF FIGURES

The following Figures are presented for the purpose of illustratingselected embodiments of this disclosure. It is understood thatembodiments in this disclosure are not limited by these figures; forexample, the precise number of vessels shown in FIGS. 6 and 7 , or thearrangement of vessels is not limiting.

FIG. 1 compares the Unsaturation Ratio ‘UR’ for Examples 1-6, relativeto Comparatives Q through V and 1 through 5.

FIG. 2 displays cosine of phase angle cos δ as a function of weightedfrequency a_(M)ω for Example 1 and comparatives T3, R2 and S2. Solidlines depict the best fits obtained using a 33-mode generalized Maxwellmodel which were used for interpolating the linear rheology parametercos δ_(a) _(M) _(ω) at a_(M)ω=0.1 rad/s.

FIG. 3 presents a graphical representation of the dimensionlessnonlinear rheology integrated network parameter, Δ_(int.) for linearethylene interpolymers; specifically, comparatives T1 through T3 and 5a.The dashed lines are the predicted response of linear ethyleneinterpolymers having polydispersities equivalent to the comparativesample. For these linear interpolymers, the network parameter Δ_(int.)is less than 0.01. In the inset, the dotted loop shows the viscousLissajous-Bowditch of Comparative example 5a at a strain-amplitude of193% or a γ₀ cos δ_(a) _(M) _(ω) of 0.50. The straight lines visualizethe obtained instantaneous dynamic viscosities at maximum strain-rate(η′_(L)) and at minimum strain-rate (η′_(M)) as the slope of a secantline crossing the viscous Lissajous-Bowditch loop at the maximumstrain-rate and the slope of a tangent line touching the viscousLissajous-Bowditch loop at a strain-rate of zero.

FIG. 4 presents a graphical representation of the dimensionlessnonlinear rheology integrated network parameter, Δ_(int.) for Example 1.The solid line is the best fit obtained using the equationINF=−Kζ^(1.45)(ζ^(a)−C) to the data points with a third-harmonic ratioI_(3/1) of at least 0.1%. The dashed line is the predicted response of alinear ethylene interpolymer with an identical polydispersity. As can beseen, the network parameter Δ_(int.) is positive and significantlylarger than 0.01. In the inset, the dotted loop shows the viscousLissajous-Bowditch of Inventive example 1 at a strain-amplitude of 193%or a γ₀ cos δ_(a) _(M) _(ω) of 0.69. The straight lines visualize theobtained instantaneous dynamic viscosities at maximum strain-rate(η′_(L)) and at minimum strain-rate (η′_(M)) as the slope of a secantline crossing the viscous Lissajous-Bowditch loop at the maximumstrain-rate and the slope of a tangent line touching the viscousLissajous-Bowditch loop at a strain-rate of zero.

FIG. 5 Compares the dimensionless nonlinear rheology integrated networkparameter Δ_(int.) of Examples 1, 2 and 8 with Comparatives 5a, 3a, R1through R3, Q1 through Q4, S1 through S4, T2, V2a, V3, V4, U1 and Resin34 as a function of normalized molecular weight

${Z = \frac{M_{w}}{M_{e}}}.$The area enclosed by the solid lines depicts the region defined by theinequality [0.01×(Z−50)^(0.78)≤Δ_(int.)≤0.01×(Z−60)^(0.78)].

FIG. 6 illustrates embodiments of a continuous solution polymerizationprocess employing one CSTR reactor (vessel 11 a) and one tubular reactor(vessel 17).

FIG. 7 illustrates embodiments of a continuous solution polymerizationprocess employing two CSTR reactors (vessels 111 a and 112 a) and onetubular reactor (vessel 117). The two CSTR may be operated in series orparallel modes.

FIG. 8 SEC determined molecular weight distribution and GPC-FTIRdetermined branch content (BrF, C₆/1000C) in Example 14 and Comparative14.

FIG. 9 deconvolution of ethylene interpolymer product Example 4 into afirst, second and third ethylene interpolymer.

FIG. 10 multilayer film cold seal force (Newtons, N) as a function ofsealing temperature.

FIG. 11 multilayer film hot tack force (Newtons, N) as a function ofsealing temperature.

DEFINITION OF TERMS

Other than in the examples or where otherwise indicated, all numbers orexpressions referring to quantities of ingredients, extrusionconditions, etc., used in the specification and claims are to beunderstood as modified in all instances by the term ‘about’.Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that can vary depending upon the desired properties thatthe various embodiments desire to obtain. At the very least, and not asan attempt to limit the application of the doctrine of equivalents tothe scope of the claims, each numerical parameter should at least beconstrued, in light of the number of reported significant digits and byapplying ordinary rounding techniques. The numerical values set forth inthe specific examples are reported as precisely as possible. Anynumerical values, however, inherently contain certain errors necessarilyresulting from the standard deviation found in their respective testingmeasurements.

It should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between andincluding the recited minimum value of 1 and the recited maximum valueof 10; that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. Because the disclosednumerical ranges are continuous, they include every value between theminimum and maximum values. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations.

All compositional ranges expressed herein are limited in total to and donot exceed 100 percent (volume percent or weight percent) in practice.Where multiple components can be present in a composition, the sum ofthe maximum amounts of each component can exceed 100 percent, with theunderstanding that, and as those skilled in the art readily understand,that the amounts of the components actually used will conform to themaximum of 100 percent.

In order to form a more complete understanding of this disclosure thefollowing terms are defined and should be used with the accompanyingfigures and the description of the various embodiments throughout.

As used herein, the term “monomer” refers to a small molecule that maychemically react and become chemically bonded with itself or othermonomers to form a polymer.

As used herein, the term “α-olefin” is used to describe a monomer havinga linear hydrocarbon chain containing from 3 to 20 carbon atoms having adouble bond at one end of the chain; an equivalent term is “linearα-olefin”.

As used herein, the term “ethylene polymer”, refers to macromoleculesproduced from ethylene and optionally one or more additional monomers;regardless of the specific catalyst or specific process used to make theethylene polymer. In the polyethylene art, the one or more additionalmonomers are frequently called “comonomer(s)” and often includeα-olefins. The term “homopolymer” refers to a polymer that contains onlyone type of monomer. Common ethylene polymers include high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linearlow-density polyethylene (LLDPE), very low density polyethylene (VLDPE),ultralow density polyethylene (ULDPE), plastomer and elastomers. Theterm ethylene polymer also includes polymers produced in a high pressurepolymerization processes; non-limiting examples include low densitypolyethylene (LDPE), ethylene vinyl acetate copolymers (EVA), ethylenealkyl acrylate copolymers, ethylene acrylic acid copolymers and metalsalts of ethylene acrylic acid (commonly referred to as ionomers). Theterm ethylene polymer also includes block copolymers which may include 2to 4 comonomers. The term ethylene polymer also includes combinationsof, or blends of, the ethylene polymers described above.

The term “ethylene interpolymer” refers to a subset of polymers withinthe “ethylene polymer” group that excludes polymers produced in highpressure polymerization processes; non-limiting examples of polymerproduced in high pressure processes include LDPE and EVA (the latter isa copolymer of ethylene and vinyl acetate).

The term “heterogeneous ethylene interpolymers” refers to a subset ofpolymers in the ethylene interpolymer group that are produced using aheterogeneous catalyst formulation; non-limiting examples of whichinclude Ziegler-Natta or chromium catalysts.

The term “homogeneous ethylene interpolymer” refers to a subset ofpolymers in the ethylene interpolymer group that are produced usinghomogeneous catalyst formulations. Typically, homogeneous ethyleneinterpolymers have narrow molecular weight distributions, for exampleSize Exclusion Chromatography (SEC)

$\frac{M_{w}}{M_{n}}$values of less than 2.8; M_(w) and M_(n) refer to weight and numberaverage molecular weights, respectively. In contrast, the

$\frac{M_{w}}{M_{n}}$of heterogeneous ethylene interpolymers are typically greater than the

$\frac{M_{w}}{M_{n}}$of homogeneous ethylene interpolymers. In general, homogeneous ethyleneinterpolymers also have a narrow comonomer distribution, i.e. eachmacromolecule within the molecular weight distribution has a similarcomonomer content. Frequently, the composition distribution breadthindex “CDBI” is used to quantify how the comonomer is distributed withinan ethylene interpolymer, as well as to differentiate ethyleneinterpolymers produced with different catalysts or processes. The“CDBI₅₀” is defined as the percent of ethylene interpolymer whosecomposition is within 50% of the median comonomer composition; thisdefinition is consistent with that described in U.S. Pat. No. 5,206,075assigned to Exxon Chemical Patents Inc. The CDBI₅₀ of an ethyleneinterpolymer can be calculated from TREF curves (Temperature RisingElution Fractionation); the TREF method is described in Wild, et al., J.Polym. Sci., Part B, Polym. Phys., 1982, 20, pp 441-455. Typically, theCDBI₅₀ of homogeneous ethylene interpolymers are greater than about 70%.In contrast, the CDBI₅₀ of α-olefin containing heterogeneous ethyleneinterpolymers are generally lower than the CDBI₅₀ of homogeneousethylene interpolymers. A blend of two or more homogeneous ethyleneinterpolymers (that differ in comonomer content) may have a CDBI₅₀ lessthan 70%; in this disclosure such a blend may be referred to as ahomogeneous blend or homogeneous composition. Similarly, a blend of twoor more homogeneous ethylene interpolymers (that differ in weightaverage molecular weight M_(w)) may have a

${\frac{M_{w}}{M_{n}} \geq {2.8}};$in this disclosure such a blend may be referred to as a homogeneousblend or homogeneous composition.

In this disclosure, the term “homogeneous ethylene interpolymer” refersto both linear homogeneous ethylene interpolymers and substantiallylinear homogeneous ethylene interpolymers. In the art, linearhomogeneous ethylene interpolymers are generally assumed to have no longchain branches or an undetectable amount of long chain branches; whilesubstantially linear ethylene interpolymers are generally assumed tohave low levels of long-chain branching (i.e. much less than 1 longchain branch per 1000 carbon atoms as described by Shroff and Mavridisin Macromolecules 1999, 32, 8454-8464). These LCB levels are far belowthe detection limits of analytical methods such as solution viscometry,size-exclusion chromatography and NMR spectrometry. However, LCBstructures at these levels have a profound impact on melt rheology andforming behavior of polymeric materials. A long chain branch ismacromolecular in nature, i.e. a branch that has a length greater thanthe critical molecular weight for entanglement (i.e. 2 to 3 time largerthan M_(e)≅900 g/mol for PE homopolymer) up to a branch that has alength similar to that of the macromolecule backbone that the long chainbranch is attached to (see Doerpinghaus and Baird, Journal of Rheology2003, 47, 717-736).

In this disclosure, the term ‘homogeneous catalyst’ is defined by thecharacteristics of the polymer produced by the homogeneous catalyst.More specifically, a catalyst is a homogeneous catalyst if it produces ahomogeneous ethylene interpolymer that has a narrow molecular weightdistribution (SEC-determined

$\frac{M_{w}}{M_{n}}$values of less than 2.8) and a narrow comonomer distribution(CDBI₅₀>70%). Homogeneous catalysts are well known in the art. Twosubsets of the homogeneous catalyst genus include unbridged metallocenecatalysts and bridged metallocene catalysts. Unbridged metallocenecatalysts are characterized by two bulky ligands bonded to the catalyticmetal, a non-limiting example includes bis(isopropyl-cyclopentadienyl)hafnium dichloride. In bridged metallocene catalysts the two bulkyligands are covalently bonded (bridged) together, a non-limiting exampleincludes diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfuorenyl)hafnium dichloride; wherein the diphenylmethylene group bonds, orbridges, the cyclopentadienyl and fluorenyl ligands together. Twoadditional subsets of the homogeneous catalyst genus include unbridgedand bridged single site catalysts. In this disclosure, single sitecatalysts are characterized as having only one bulky ligand bonded tothe catalytic metal. A non-limiting example of an unbridged single sitecatalyst includes cyclopentadienyl tri(tertiary butyl)phosphiniminetitanium dichloride. A non-limiting example of a bridged single sitecatalyst includes [C₅(CH₃)₄—Si(CH₃)₂—N(tBu)] titanium dichloride, wherethe —Si(CH₃)₂ group functions as the bridging group.

Herein, the term “polyolefin” includes ethylene polymers and propylenepolymers; non-limiting examples of propylene polymers include isotactic,syndiotactic and atactic propylene homopolymers, random propylenecopolymers containing at least one comonomer (e.g. α-olefins) and impactpolypropylene copolymers or heterophasic polypropylene copolymers.

The term “thermoplastic” refers to a polymer that becomes liquid whenheated, will flow under pressure and solidify when cooled. Thermoplasticpolymers include ethylene polymers as well as other polymers used in theplastic industry; non-limiting examples of other polymers commonly usedin film applications include barrier resins (EVOH), tie resins,polyethylene terephthalate (PET), polyamides and the like.

As used herein the term “monolayer film” refers to a film containing asingle layer of one or more thermoplastics.

As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or“hydrocarbyl group” refers to linear, branched, or cyclic, aliphatic,olefinic, acetylenic and aryl (aromatic) radicals comprising hydrogenand carbon that are deficient by one hydrogen.

As used herein, an “alkyl radical” includes linear, branched and cyclicparaffin radicals that are deficient by one hydrogen radical;non-limiting examples include methyl (—CH₃) and ethyl (—CH₂CH₃)radicals. The term “alkenyl radical” refers to linear, branched andcyclic hydrocarbons containing at least one carbon-carbon double bondthat is deficient by one hydrogen radical.

As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyland other radicals whose molecules have an aromatic ring structure;non-limiting examples include naphthylene, phenanthrene and anthracene.An “arylalkyl” group is an alkyl group having an aryl group pendantthere from; non-limiting examples include benzyl, phenethyl andtolylmethyl; an “alkylaryl” is an aryl group having one or more alkylgroups pendant there from; non-limiting examples include tolyl, xylyl,mesityl and cumyl.

As used herein, the phrase “heteroatom” includes any atom other thancarbon and hydrogen that can be bound to carbon. A“heteroatom-containing group” is a hydrocarbon radical that contains aheteroatom and may contain one or more of the same or differentheteroatoms. In one embodiment, a heteroatom-containing group is ahydrocarbyl group containing from 1 to 3 atoms selected from the groupconsisting of boron, aluminum, silicon, germanium, nitrogen,phosphorous, oxygen and sulfur. Non-limiting examples ofheteroatom-containing groups include radicals of imines, amines, oxides,phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines,thioethers, and the like. The term “heterocyclic” refers to ring systemshaving a carbon backbone that comprise from 1 to 3 atoms selected fromthe group consisting of boron, aluminum, silicon, germanium, nitrogen,phosphorous, oxygen and sulfur.

As used herein the term “unsubstituted” means that hydrogen radicals arebounded to the molecular group that follows the term unsubstituted. Theterm “substituted” means that the group following this term possessesone or more moieties that have replaced one or more hydrogen radicals inany position within the group; non-limiting examples of moieties includehalogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxylgroups, amine groups, phosphine groups, alkoxy groups, phenyl groups,naphthyl groups, C₁ to C₁₀ alkyl groups, C₂ to C₁₀ alkenyl groups, andcombinations thereof. Non-limiting examples of substituted alkyls andaryls include acyl radicals, alkylamino radicals, alkoxy radicals,aryloxy radicals, alkylthio radicals, dialkylamino radicals,alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals,alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylaminoradicals, arylamino radicals and combinations thereof.

Herein the term “R1” and its superscript form “^(R1)” refers to a firstreactor in a continuous solution polymerization process; it beingunderstood that R1 is different from the symbol R¹; the latter is usedin chemical formula, e.g. representing a hydrocarbyl group. Similarly,the term “R2” and it's superscript form “^(R2)” refers to a secondreactor, and; the term “R3” and it's superscript form “^(R3)” refers toa third reactor.

As used herein, the term “oligomers” refers to an ethylene polymer oflow molecular weight, e.g., an ethylene polymer with a weight averagemolecular weight (Mw) of about 2000 to 3000 daltons. Other commonly usedterms for oligomers include “wax” or “grease”. As used herein, the term“light-end impurities” refers to chemical compounds with relatively lowboiling points that may be present in the various vessels and processstreams within a continuous solution polymerization process;non-limiting examples include, methane, ethane, propane, butane,nitrogen, CO₂, chloroethane, HCl, etc.

DETAILED DESCRIPTION

There is a need to improve the continuous solution polymerizationprocess. For example, to increase the molecular weight of the ethyleneinterpolymer produced at a given reactor temperature. In addition, insolution polymerization there is a need for catalyst formulations thatare very efficient at incorporating one or more α-olefins into thepropagating macromolecular chain. Expressed in different manner, thereis a need for catalyst formulations that produce an ethylene/α-olefincopolymer, having a specific density, at a lower (α-olefin/ethylene)ratio in the reactor feed. In addition, there is a need for ethyleneinterpolymer products that upon conversion into manufactured articleshave improved properties.

In the embodiments disclosed herein, ‘a bridged metallocene catalystformulation’ was employed in at least one solution polymerizationreactor. This catalyst formulation included a bulky ligand-metalcomplex, ‘Component A’, defined by Formula (I).

In Formula (I): non-limiting examples of M include Group 4 metals, i.e.titanium, zirconium and hafnium; non-limiting examples of G includeGroup 14 elements, carbon, silicon, germanium, tin and lead; Xrepresents a halogen atom, fluorine, chlorine, bromine or iodine; the Regroups are independently selected from a hydrogen atom, a C₁₋₂₀hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxideradical (these radicals may be linear, branched or cyclic or furthersubstituted with halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀ alkoxyradicals, C₆₋₁₀ aryl or aryloxy radicals); R₁ represents a hydrogenatom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, a C₆₋₁₀ aryloxide radical or alkylsilyl radicals containing at least one siliconatom and C₃₋₃₀ carbon atoms; R₂ and R₃ are independently selected from ahydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, aC₆₋₁₀ aryl oxide radical or alkylsilyl radicals containing at least onesilicon atom and C₃₋₃₀ carbon atoms, and; R₄ and R₅ are independentlyselected from a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀alkoxy radical a C₆₋₁₀ aryl oxide radical, or alkylsilyl radicalscontaining at least one silicon atom and C₃₋₃₀ carbon atoms.

In the art, a commonly used term for the X(R₆) group shown in Formula(I) is ‘leaving group’, i.e. any ligand that can be abstracted fromFormula (I) forming a catalyst species capable of polymerizing one ormore olefin(s). An equivalent term for the X(R₆) group is an‘activatable ligand’. Further non-limiting examples of the X(R₆) groupshown in Formula (I) include weak bases such as amines, phosphines,ethers, carboxylates and dienes. In another embodiment, the two Regroups may form part of a fused ring or ring system.

Further embodiments of component A include structural, optical orenantiomeric isomers (meso and racemic isomers) and mixtures thereof ofthe structure shown in Formula (I). While not to be construed aslimiting, two species of component A include:diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdichloride having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂],and; diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂].

In the embodiments disclosed herein, ‘a bridged metallocene catalystformulation’ was employed in: (i) a first reactor to produce a firstethylene interpolymer, or (ii) a first and third reactor, to produce afirst and third ethylene interpolymer, or (iii) a first and secondreactor, to produce a first and second ethylene interpolymer, or (iv) afirst, second and third solution polymerization reactor, to produce afirst, second and third ethylene interpolymer. The first and secondreactors may be operated in series or parallel mode. In series mode theeffluent from the first reactor flows directly into the second reactor.In contrast, in parallel mode the effluent from the first reactorby-passes the second reactor and the effluent from the first and secondreactor are combined downstream of the second reactor.

A wide variety of catalyst formulations may be employed in the optionalthird reactor. Non-limiting examples of the catalyst formulationemployed in the third reactor include the bridged metallocene catalystformulation described above, the unbridged single site catalystformulation described below, a homogeneous catalyst formulationcomprising a bulky ligand-metal complex that is not a member of thegenera defined by Formula (I) (above), or Formula (II) (below), or aheterogeneous catalyst formulation. Non-limiting examples ofheterogeneous catalyst formulations include Ziegler-Natta or chromiumcatalyst formulations.

In Comparative 1 samples disclosed herein, e.g. Comparative 1a and 1b,‘an unbridged single site catalyst formulation’ was employed in at leastone solution polymerization reactor. This catalyst formulation includeda bulky ligand-metal complex, hereinafter ‘Component C’, defined byFormula (II).(L^(A))_(a)M(PI)_(b)(Q)_(n)  (II)

In Formula (II): (L^(A)) represents a bulky ligand; M represents a metalatom; PI represents a phosphinimine ligand; Q represents a leavinggroup; a is 0 or 1; b is 1 or 2; (a+b)=2; n is 1 or 2, and; the sum of(a+b+n) equals the valance of the metal M. Non-limiting examples of M inFormula (II) include Group 4 metals, titanium, zirconium and hafnium.

Non-limiting examples of the bulky ligand L^(A) in Formula (II) includeunsubstituted or substituted cyclopentadienyl ligands orcyclopentadienyl-type ligands, heteroatom substituted and/or heteroatomcontaining cyclopentadienyl-type ligands. Additional non-limitingexamples include, cyclopentaphenanthreneyl ligands, unsubstituted orsubstituted indenyl ligands, benzindenyl ligands, unsubstituted orsubstituted fluorenyl ligands, octahydrofluorenyl ligands,cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenylligands, azulene ligands, pentalene ligands, phosphoyl ligands,phosphinimine, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands,borabenzene ligands and the like, including hydrogenated versionsthereof, for example tetrahydroindenyl ligands. In other embodiments,L^(A) may be any other ligand structure capable of η-bonding to themetal M, such embodiments include both η³-bonding and η⁵-bonding to themetal M. In other embodiments, L^(A) may comprise one or moreheteroatoms, for example, nitrogen, silicon, boron, germanium, sulfurand phosphorous, in combination with carbon atoms to form an open,acyclic, or a fused ring, or ring system, for example, aheterocyclopentadienyl ancillary ligand. Other non-limiting embodimentsfor L^(A) include bulky amides, phosphides, alkoxides, aryloxides,imides, carbolides, borollides, porphyrins, phthalocyanines, corrins andother polyazomacrocycles.

The phosphinimine ligand, PI, is defined by Formula (III):(R^(p))₃P═N—  (III)

wherein the R^(p) groups are independently selected from: a hydrogenatom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstitutedor substituted with one or more halogen atom(s); a C₁₋₈ alkoxy radical;a C₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silylradical of formula —Si(R^(s))₃, wherein the R^(s) groups areindependently selected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxyradical, a C₆₋₁₀ aryl radical, a C₆₋₁₀ aryloxy radical, or a germanylradical of formula —Ge(R^(G))₃, wherein the R^(G) groups are defined asR^(s) is defined in this paragraph.

The leaving group Q is any ligand that can be abstracted from Formula(II) forming a catalyst species capable of polymerizing one or moreolefin(s). In some embodiments, Q is a monoanionic labile ligand havinga sigma bond to M. Depending on the oxidation state of the metal, thevalue for n is 1 or 2 such that Formula (II) represents a neutral bulkyligand-metal complex. Non-limiting examples of Q ligands include ahydrogen atom, halogens, C₁₋₂₀ hydrocarbyl radicals, C₁₋₂₀ alkoxyradicals, C₅₋₁₀ aryl oxide radicals; these radicals may be linear,branched or cyclic or further substituted by halogen atoms, C₁₋₁₀ alkylradicals, C₁₋₁₀ alkoxy radicals, C₆₋₁₀ arly or aryloxy radicals. Furthernon-limiting examples of Q ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms. In another embodiment, two Q ligands may formpart of a fused ring or ring system.

Further embodiments of Component C include structural, optical orenantiomeric isomers (meso and racemic isomers) and mixtures thereof ofthe bulky ligand-metal complex shown in Formula (II).

While not to be construed as limiting, two species of component Cinclude: cyclopentadienyl tri(tertiary butyl) phosphinimine titaniumdichloride having the molecular formula [Cp[(t-Bu)₃PN]TiCl₂], and;cyclopentadienyl tri(isopropyl)phosphinimine titanium dichloride havingthe molecular formula [Cp[(isopropyl)₃PN]TiCl₂].

The bridged metallocene catalyst formulation contains a component A(defined above), a component M^(A), a component B^(A) and a componentP^(A). Components M, B and P are defined below and the superscript“^(A)” denotes that fact that the respective component was part of thecatalyst formulation containing component A, i.e. the bridgedmetallocene catalyst formulation.

In this disclosure Comparative ethylene interpolymer products wereprepared by employing an unbridged single site catalyst formulation. Inthese Comparative samples, the unbridged single site catalystformulation replaced the bridged metallocene catalyst formulation in thefirst polymerization reactor, or the first and second polymerizationreactor(s), or the first, second and third polymerization reactors. Theunbridged single site catalyst formulation contains a component C(defined above), a component M^(C), a component B^(C) and a componentP^(C). Components M, B and P are defined below and the superscript“^(C)” denoted that fact that the respective component was part of thecatalyst formulation containing component C, i.e. the unbridged singlesite catalyst formulation.

The catalyst components M, B and P were independently selected for eachcatalyst formulation. To be more clear: components M^(A) and M^(C) may,or may not, be the same chemical compound; components B^(A) and B^(C)may, or may not, be the same chemical compound, and; components P^(A)and P^(C) may, or may not, be the same chemical compound. Further,catalyst activity was optimized by independently adjusting the moleratios of the components in each catalyst formulation.

Components M, B and P were not particularly limited, i.e. a wide varietyof components can be used as described below.

Component M functioned as a co-catalyst that activated component A orcomponent C, into a cationic complex that effectively polymerizedethylene, or mixtures of ethylene and α-olefins, producing highmolecular weight ethylene interpolymers. In the bridged metallocenecatalyst formulation and the unbridged single site catalyst formulationthe respective component M was independently selected from a variety ofcompounds and those skilled in the art will understand that theembodiments in this disclosure are not limited to the specific chemicalcompound disclosed. Suitable compounds for component M included analumoxane co-catalyst (an equivalent term for alumoxane is aluminoxane).Although the exact structure of an alumoxane co-catalyst was uncertain,subject matter experts generally agree that it was an oligomeric speciesthat contain repeating units of the general Formula (IV):(R)₂AlO—(Al(R)—O)_(n)—Al(R)₂  (IV)

where the R groups may be the same or different linear, branched orcyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n isfrom 0 to about 50. A non-limiting example of an alumoxane was methylaluminoxane (or MMAO-7) wherein each R group in Formula (IV) is a methylradical.

Component B was an ionic activator. In general, ionic activators arecomprised of a cation and a bulky anion; wherein the latter issubstantially non-coordinating.

In the bridged metallocene catalyst formulation and the unbridged singlesite catalyst formulation the respective component B was independentlyselected from a variety of compounds and those skilled in the art willunderstand that the embodiments in this disclosure are not limited tothe specific chemical compound disclosed. Non-limiting examples ofcomponent B were boron ionic activators that are four coordinate withfour ligands bonded to the boron atom. Non-limiting examples of boronionic activators included the following Formulas (V) and (VI) shownbelow;[R⁵]⁺[B(R⁷)₄]⁻  (V)

where B represented a boron atom, R⁵ was an aromatic hydrocarbyl (e.g.triphenyl methyl cation) and each R⁷ was independently selected fromphenyl radicals which were unsubstituted or substituted with from 3 to 5substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicalswhich were unsubstituted or substituted by fluorine atoms; and a silylradical of formula —Si(R⁹)₃, where each R⁹ was independently selectedfrom hydrogen atoms and C₁₋₄ alkyl radicals, and; compounds of formula(VI);[(R⁸)_(t)ZH]⁺[B(R⁷)₄]⁺  (VI)

where B was a boron atom, H was a hydrogen atom, Z was a nitrogen orphosphorus atom, t was 2 or 3 and R⁸ was selected from C₁₋₈ alkylradicals, phenyl radicals which were unsubstituted or substituted by upto three C₁₋₄ alkyl radicals, or one R⁸ taken together with the nitrogenatom may form an anilinium radical and R⁷ was as defined above inFormula (VI).

In both Formula (V) and (VI), a non-limiting example of R⁷ was apentafluorophenyl radical. In general, boron ionic activators may bedescribed as salts of tetra(perfluorophenyl) boron; non-limitingexamples include anilinium, carbonium, oxonium, phosphonium andsulfonium salts of tetra(perfluorophenyl)boron with anilinium and trityl(or triphenylmethylium). Additional non-limiting examples of ionicactivators included: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate,benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercialionic activators included N,N-dimethylaniliniumtetrakispentafluorophenyl borate, and triphenylmethyliumtetrakispentafluorophenyl borate.

Component P is a hindered phenol and is an optional component in therespective catalyst formulation. In the bridged metallocene catalystformulation and the unbridged single site catalyst formulation therespective component P was independently selected from a variety ofcompounds and those skilled in the art will understand that theembodiments in this disclosure are not limited to the specific chemicalcompound disclosed. Non-limiting example of hindered phenols includedbutylated phenolic antioxidants, butylated hydroxytoluene,2,4-di-tertiarybutyl-6-ethyl phenol, 4,4′-methylenebis(2,6-di-tertiary-butylphenol), 1,3, 5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

As fully described below, a highly active bridged metallocene catalystformulation was produced by optimizing the quantity and mole ratios ofthe four components in the formulation, i.e., component A, componentM^(A), component B^(A) and optionally component P^(A). Where highlyactive means a very large amount of ethylene interpolymer is producedfrom a very small amount of catalyst formulation. Similarly, a highlyactive unbridged single site catalyst formulation (comparative catalystformulation) was produced by optimizing the quantity and mole ratios ofthe four components in the formulation; i.e., component C, componentM^(C), component B^(C) and optionally component P^(C).

In this disclosures, heterogeneous catalyst formulations may be employedin the optional third reactor to synthesize the third ethyleneinterpolymer. Non-limiting examples of heterogeneous catalystformulations include Ziegler-Natta and chromium catalyst formulations.Non-limiting examples of Ziegler-Natta catalyst formulations include ‘anin-line Ziegler-Natta catalyst formulation’ or ‘a batch Ziegler-Nattacatalyst formulation’. The term ‘in-line’ refers to the continuoussynthesis of a small quantity of active Ziegler-Natta catalyst andimmediately injecting this catalyst into the third reactor, whereinethylene and one or more optional α-olefins were polymerized to form theoptional third ethylene interpolymer. The term ‘batch’ refers to thesynthesis of a much larger quantity of catalyst or procatalyst in one ormore mixing vessels that were external to, or isolated from, thecontinuously operating solution polymerization process. Once prepared,the batch Ziegler-Natta catalyst formulation, or batch Ziegler-Nattaprocatalyst, was transferred to a catalyst storage tank. The term‘procatalyst’ referred to an inactive catalyst formulation (inactivewith respect to ethylene polymerization); the procatalyst was convertedinto an active catalyst by adding an alkyl aluminum co-catalyst. Asneeded, the procatalyst was pumped from the storage tank to at least onecontinuously operating reactor, wherein an active catalyst polymerizesethylene and one or more optional α-olefins to form an ethyleneinterpolymer. The procatalyst may be converted into an active catalystin the reactor or external to the reactor.

A wide variety of chemical compounds can be used to synthesize an activeZiegler-Natta catalyst formulation. The following describes variouschemical compounds that may be combined to produce an activeZiegler-Natta catalyst formulation. Those skilled in the art willunderstand that the embodiments in this disclosure are not limited tothe specific chemical compound disclosed.

An active Ziegler-Natta catalyst formulation may be formed from: amagnesium compound, a chloride compound, a metal compound, an alkylaluminum co-catalyst and an aluminum alkyl. In this disclosure, the term“component (v)” is equivalent to the magnesium compound, the term“component (vi)” is equivalent to the chloride compound, the term“component (vii)” is equivalent to the metal compound, the term“component (viii)” is equivalent to the alkyl aluminum co-catalyst andthe term “component (ix)” is equivalent to the aluminum alkyl. As willbe appreciated by those skilled in the art, Ziegler-Natta catalystformulations may contain additional components; a non-limiting exampleof an additional component is an electron donor, e.g. amines or ethers.

A non-limiting example of an active in-line Ziegler-Natta catalystformulation can be prepared as follows. In the first step, a solution ofa magnesium compound (component (v)) is reacted with a solution of thechloride compound (component (vi)) to form a magnesium chloride supportsuspended in solution. Non-limiting examples of magnesium compoundsinclude Mg(R¹)₂; wherein the R¹ groups may be the same or different,linear, branched or cyclic hydrocarbyl radicals containing 1 to 10carbon atoms. Non-limiting examples of chloride compounds include R²Cl;wherein R² represents a hydrogen atom, or a linear, branched or cyclichydrocarbyl radical containing 1 to 10 carbon atoms. In the first step,the solution of magnesium compound may also contain an aluminum alkyl(component (ix)). Non-limiting examples of aluminum alkyl includeAl(R³)₃, wherein the R³ groups may be the same or different, linear,branched or cyclic hydrocarbyl radicals containing from 1 to 10 carbonatoms. In the second step a solution of the metal compound (component(vii)) is added to the solution of magnesium chloride and the metalcompound is supported on the magnesium chloride. Non-limiting examplesof suitable metal compounds include M(X)_(n) or MO(X)_(n); where Mrepresents a metal selected from Group 4 through Group 8 of the PeriodicTable, or mixtures of metals selected from Group 4 through Group 8; Orepresents oxygen, and; X represents chloride or bromide; n is aninteger from 3 to 6 that satisfies the oxidation state of the metal.Additional non-limiting examples of suitable metal compounds includeGroup 4 to Group 8 metal alkyls, metal alkoxides (which may be preparedby reacting a metal alkyl with an alcohol) and mixed-ligand metalcompounds that contain a mixture of halide, alkyl and alkoxide ligands.In the third step a solution of an alkyl aluminum co-catalyst (component(viii)) is added to the metal compound supported on the magnesiumchloride. A wide variety of alkyl aluminum co-catalysts are suitable, asexpressed by Formula (VII):Al(R⁴)_(p)(OR⁵)_(q)(X)_(r)  (VII)

wherein the R⁴ groups may be the same or different, hydrocarbyl groupshaving from 1 to 10 carbon atoms; the OR⁵ groups may be the same ordifferent, alkoxy or aryloxy groups wherein R⁵ is a hydrocarbyl grouphaving from 1 to 10 carbon atoms bonded to oxygen; X is chloride orbromide, and; (p+q+r)=3, with the proviso that p is greater than 0.Non-limiting examples of commonly used alkyl aluminum co-catalystsinclude trimethyl aluminum, triethyl aluminum, tributyl aluminum,dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminumbutoxide, dimethyl aluminum chloride or bromide, diethyl aluminumchloride or bromide, dibutyl aluminum chloride or bromide and ethylaluminum dichloride or dibromide.

The process described in the paragraph above, to synthesize an activein-line Ziegler-Natta catalyst formulation, can be carried out in avariety of solvents; non-limiting examples of solvents include linear orbranched C₅ to C₁₂ alkanes or mixtures thereof.

To produce an active in-line Ziegler-Natta catalyst formulation thequantity and mole ratios of the five components, (v) through (ix), areoptimized as described below.

Additional embodiments of heterogeneous catalyst formulations includeformulations where the “metal compound” is a chromium compound;non-limiting examples include silyl chromate, chromium oxide andchromocene. In some embodiments, the chromium compound is supported on ametal oxide such as silica or alumina. Heterogeneous catalystformulations containing chromium may also include co-catalysts;non-limiting examples of co-catalysts include trialkylaluminum,alkylaluminoxane and dialkoxyalkylaluminum compounds and the like.

In this disclosure, the bridged metallocene catalyst formulationproduced solution process ethylene interpolymer products having a uniqueunsaturation ratio, UR.

Table 1 discloses the amount of Internal, Side Chain and Terminalunsaturations per 100 carbons (100C) in the Examples of this disclosure,relative to Comparatives, i.e. the amount of trans-vinylene, vinylideneand terminal vinyl groups as measured according to ASTM D3124-98 andASTM D6248-98. Table 1 also discloses the dimensionless ‘UnsaturationRatio’, ‘UR’, as defined by the following equation

$\begin{matrix}{{UR} = {\left( {{SC^{U}} - T^{U}} \right)/T^{U}}} & {{Eq}.({UR})}\end{matrix}$

where SC^(U) are the side chain unsaturations and T^(U) are the terminalunsaturations. Graphically, FIG. 1 compares the average UR values forExamples and Comparatives. Statistically, the Examples (Examples 1through 6) have a significantly different average UR value, relative toall Comparatives. For example, the average UR value for Examples 1through 6 was −0.116±0.087 and the average UR value for Comparative Q1through Q4 was 0.085±0.014; these average UR values were significantlydifferent based on a t-test assuming equal variances, i.e. the t-stat of4.51 exceeded the two tail t-critical of 2.31 and the two tail P-valueof 0.00197 was less than 0.05. Comparative Q were commercial productscalled Queo available from Borealis, Vienna, Austria; specifically,Comparative Q1 was Queo 0201, Comparative Q2 was Queo 8201, ComparativeQ3 was Queo 0203 and Comparative Q4 was Queo 1001. Queo products areethylene/1-octene copolymers, believed to be produced in a solutionpolymerization process employing one reactor and a metallocene catalystformulation.

Statistically, the average UR value of Examples 1 through 6 was alsosignificantly different from Comparative R, Comparative S, ComparativeT, Comparative U, Comparative V, Comparative 1, Comparative 2,Comparative 3, Comparative 4 and Comparative 5. As shown in Table 1 andFIG. 1 , the average UR of Comparative R was 1.349±0.907, this was theaverage of 7-samples of commercial products called Affinity availablefrom The Dow Chemical Company, Midland, Mich.; specifically, AffinityPL1880 (3-samples), Affinity PF1140, Affinity PF1142 and AffinityPL1881. The Affinity samples were ethylene/1-octene copolymers believedto be produced in a solution polymerization process employing onereactor and a single site catalyst formulation. The average UR ofComparative S was 0.1833±0.0550, i.e. an average of 5-samples ofcommercial products called Enable available from ExxonMobil ChemicalCompany, Spring, Tex.; specifically, Enable 27-03CH (3-samples) andEnable 20-05 (2-samples). Enable products were ethylene/1-hexenecopolymers, believed to be produced in a gas phase process employing onereactor and a metallocene catalyst formulation. The average UR ofComparative T was −0.6600±0.1306, i.e. an average of 48-samples ofcommercial products called Exceed available from ExxonMobil ChemicalCompany, Spring, Tex.; specifically, Exceed 1018 (26-samples), Exceed1023 (4-samples), Exceed 1015 (3-samples), Exceed 4518 (3-samples),Exceed 3518(4-samples), Exceed 1012 (3-samples), Exceed 1318CA(2-samples), Exceed 3812, Exceed 1023DA and Exceed 2718CB. Exceedproducts were ethylene/1-hexene copolymers believed to be produced in agas phase process employing one reactor and a metallocene catalystformulation. Comparative U, having a UR value of −0.667, was acommercial product called Elite AT 6202 available from The Dow ChemicalCompany, Midland, Mich. Elite AT 6202 was an ethylene/1-hexenecopolymer, believed to be produced in a dual reactor solution processemploying at least one homogeneous catalyst formulation. The average URof Comparative V was −0.8737±10.0663, i.e. an average of 25-samples ofcommercial products called Elite available from The Dow ChemicalCompany, Midland, Mich.; specifically, Elite 5400 (12-samples), Elite5100 (4-samples), Elite 5110 (2-samples), Elite 5230 (2-samples), Elite5101 and Elite 5500. Elite products were ethylene/1-octene copolymersbelieved to be produced in a solution polymerization process employing asingle site catalyst formulation in a first reactor and a batchZiegler-Natta catalyst formulation in a second reactor. The average URof Comparative 1 was −0.4374±0.1698, i.e. an average of 61-samples of acommercial product called SURPASS FPs117 available from NOVA ChemicalsCorporation, Calgary, Alberta. SURPASS FPs117 was an ethylene/1-octenecopolymer produced in a solution polymerization process employing asingle site catalyst formulation. The average UR of Comparative 2 was−0.5000±0.1000, i.e. an average of 3-samples of an experimental productmanufactured by NOVA Chemicals Corporation, Calgary, Alberta.Comparative 2a, 2b and 2c were ethylene/1-octene copolymers (about 0.917g/cc and about 1.0 I₂) produced in a solution polymerization processemploying a bridged metallocene catalyst formulation in a first reactorand an unbridged single site catalyst formulation in a second reactor.The average UR of Comparative 3 was −0.8548±0.0427, i.e. an average of4-samples of an experimental product manufactured by NOVA ChemicalsCorporation, Calgary, Alberta. Comparative 3a, 3b, 3c and 3d wereethylene/1-octene copolymers (about 0.917 g/cc and about 1.0 I₂)produced in a solution polymerization process employing a bridgedmetallocene catalyst formulation in a first reactor and an in-lineZiegler-Natta catalyst formulation in a second reactor. The average URof Comparative 4 was −0.8633±0.0470, i.e. an average of 21-samples ofcommercial products called SURPASS available from NOVA ChemicalsCorporation, Calgary, Alberta; specifically, SURPASS SPs116 (6-samples),SURPASS SPsK919 (5-samples), SURPASS VPsK114 (3-samples) and SURPASSVPsK914 (7-samples) were ethylene/1-octene copolymers produced in asolution polymerization process employing a single site catalystformulation in a first reactor and an in-line Ziegler-Natta catalystformulation in a second reactor. The average UR of Comparative 5 was−0.8687±0.0296, i.e. an average of 137-samples of a commercial productcalled SCLAIR FP120 available from NOVA Chemicals Corporation, Calgary,Alberta. FP120 was an ethylene/1-octene copolymer produced in a solutionpolymerization process employing an in-line Ziegler-Natta catalystformulation.

As evidenced by FIG. 1 and Table 1, the UR values of Comparatives 3 to 5and Comparative V are not significantly different (the UR values rangedfrom −0.8548 to −0.8737) this is believed to reflect the fact that aZiegler-Natta catalyst was employed to manufacture at least a portion ofthese copolymers.

In this disclosure, the bridged metallocene catalyst formulationproduced ethylene interpolymer products having long chain branches,hereinafter ‘LCB’. LCB is a structural feature in polyethylenes that iswell known to those of ordinary skill in the art.

Architectural parameters such as molecular weight (MW), molecular weightdistribution (MWD) and long chain branching (LCB) have a profound impacton melt processing behavior of polymeric materials. Melt-staterheological response can be used as strong tool for characterizing thesearchitectural features. In this context, melt rheology can eithersupplement or in many cases replace existing (ultra-)dilute solutionspectroscopic and chromatographic techniques. It is well known thatlinear viscoelastic (LVE) rheological data can provide several limitingmaterial functions capable of detecting long-chain branched speciesbased on appearance of new relaxation modes due to interruption ofreptation motion by deep arm retraction (Science, 2011, 333, pp1871-1874). These LVE-based parameters can detect LCB at levels farbelow the detection limits of analytical methods such as solutionviscometry, size-exclusion chromatography and NMR spectrometry. However,it has been long well known that linear viscoelastic measures, whilestrongly related to structural features, have restricted capabilities toresolve very low content of branched species from linear chains ifpolydispersity effects are involved (Journal of Molecular Structure,1999, 485, pp 569-583).

In contrast to linear measures, oscillatory shear nonlinearviscoelasticity parameters maintain their sensitivity to very smallnumber of branching sites along the polymer chain despite the screeningeffect of polydispersity (see e.g. Journal of Rheology 2003, 47, pp717-736). In fact, the presence of long side branches is proven tointensify the elastic energy carried by the entanglement network andchange the disentanglement kinetics under and external flow-field whichcould be detected using nonlinear rheology and by application of astrong oscillatory shear flow. This disclosure outlines a very sensitiveintracycle nonlinear viscoelasticity parameter capable of detecting andquantifying LCB species in ethylene/alpha-olefin interpolymers. Byestablishing a scaling function to compensate the effect of MW andbreadth of MWD, subtle differences in the kinetics of entanglementsdissociation induced by LCB presence were detected.

In this context, this disclosure employs the strain-dependence ofintracycle shear-thickening behavior, referred to as ‘intracyclenonlinear function’, or ‘INF’ hereafter, to determine presence of LCBstructures in ethylene interpolymers according to the following steps.In the first step, a sample of an ethylene interpolymer in melt-state issubjected to an oscillating strain-wave at a fixed angular frequency andtemperature with a step-wise increasing strain-amplitude from a lowerlimit strain-amplitude to an upper limit strain-amplitude to obtain astress-wave response and corresponding viscous Lissajous-Bowditch loop(i.e. stress versus strain-rate loops) at each strain-amplitude level.In the second step, the Intracycle nonlinear function, INF, isdetermined experimentally using the instantaneous dynamic viscosities atmaximum strain-rate (η′_(L)) and at minimum strain-rate (η′_(M)) in theviscous Lissajous-Bowditch loop at each strain-amplitude level using

${INF} = \frac{\eta_{L}^{\prime} - \eta_{M}^{\prime}}{\eta_{L}^{\prime}}$(INF is dimensionless) by a rheology data processing software (e.g.Anton Paar RheoCompass). Further, in the third step, the INF obtainedfor the ethylene interpolymer product of interest is compared with areference INF predicted for a linear (non-long-chain branched) ethyleneinterpolymer product having a polydispersity (a non-limiting example ofa polydispersity measure is

$\left. \frac{M_{Z}}{M_{w}} \right)$equivalent to the said ethylene interpolymer product. In the fourthstep, presence of LCB in the ethylene interpolymer product of interestis detected according to a positive deviation from the predictedreference INF.

The instantaneous dynamic viscosities at maximum strain-rate (η′_(L))and at minimum strain-rate (η′_(M)) in a viscous Lissajous-Bowditch loopat a certain strain-amplitude level can be obtained by the stressdecomposition method introduced in Journal of rheology 2005, 49, pp747-758 and by fitting the Chebyshev polynomials of the first kind tothe viscous stress response of tested linear or long-chain branchedethylene interpolymers as described in Journal of Rheology 2008, 52, pp1427-1458. In the insets in FIGS. 3 and 4 , the obtained instantaneousdynamic viscosities at maximum strain-rate (η′_(L)) and at minimumstrain-rate (η′_(M)) are visualized as the slope of a secant linecrossing the viscous Lissajous-Bowditch loop at the maximum strain-rateand the slope of a tangent line touching the viscous Lissajous-Bowditchloop at a strain-rate of zero for Comparative example 5a and Inventiveexample 1, respectively. INF is a material function that is initiallyzero (within the linear regime) and then changes its sign to positive(intracycle shear-thickening) and/or negative values (intracycleshear-thinning) as strain amplitude increases and a nonlinear responseemerges. A dimensionless scaling function, similar to Journal ofRheology 2010, 54, pp 27-63, can be defined as ζ=γ₀ cos δ_(a) _(M) _(ω)where γ₀ is the imposed strain-amplitude and δ_(a) _(M) _(ω) is thephase-angle at a frequency of a_(M)ω=0.1 rad/s, wherein a_(M) is thetime-molecular weight superposition shift factor described below (seeFIG. 2 ), was further applied to remove the effect of linearviscoelasticity and molecular weight.

In this disclosure, the INF values of linear ethylene interpolymers wereobtained at 190° C. by applying a sinusoidal strain-wave at an angularfrequency of 0.1 rad/s over a strain amplitude range of 1-10³%. The rawwaveforms and viscous Lissajous-Bowditch loops were analyzed usingRheoCompass 1.17 software. As shown in FIG. 3 , the INF of these linearethylene interpolymers were observed to follow (Eq.1) below (INF isdimensionless):

$\begin{matrix}{{{INF}^{lin} = {{- K}{\zeta^{1.45}\left( {\zeta^{a*} - C^{*}} \right)}}};{\zeta = {\gamma_{0}{\cos\delta}_{a_{M}\omega}}}} & \left( {{Eq}.1} \right)\end{matrix}$

in which K is a constant equal 0.3722, γ₀ is the imposed strainamplitude, a_(M) is the time-molecular weight superposition shift factordefined as

$\left( \frac{M_{w}}{M_{ref}} \right)^{3.41}$where M_(w) is the SEC weight-average molecular weight and M_(ref) is areference molecular weight of 10⁵ g/mol. In Eq.1, δ_(a) _(M) _(ω) is thephase-angle at a frequency of a_(M)ω=0.1 rad/s. FIG. 2 schematicallydisplays the procedure used for interpolating the cosine of phase angleat a weighted frequency of a_(M)ω=0.1 rad/s for non-limiting examples ofExample 1 and Comparatives T3, R2 and S2 using a 33-mode generalizedMaxwell model (see Li et al. ANTEC 2014). It should be added that δ_(a)_(M) _(ω) values larger than 88.5° were not used for these calculationsand were replaced by the largest phase angle measured within a frequencyrange of 0.05-100 rad/s. Parameters a* and C* in Eq.1 were defined as afunction of the SEC-determined weight-average molecular weight M_(w) andz-average molecular weight M_(z) as follows:

$\begin{matrix}{a^{*} = {{f\left( \frac{M_{z}}{M_{w}} \right)} = \left\{ \begin{matrix}{0\ } & {\frac{M_{z}}{M_{w}} \leq {{1.6}4}} \\{{{0.8}645\ \left( {\frac{M_{z}}{M_{w}} - {1.5}} \right)} - {{0.1}198}} & {1.64 < \frac{M_{z}}{M_{w}} < {{2.2}1}} \\{\begin{matrix}{{0.5938\left( {\frac{M_{z}}{M_{w}} - {1.5}} \right)^{2}} -} \\{{1.1803\left( {\frac{M_{z}}{M_{w}} - {1.5}} \right)} + {{1.0}455}}\end{matrix}\ } & {\frac{M_{z}}{M_{w}} \geq 2.21}\end{matrix} \right.}} & \left( {{Eq}.2} \right)\end{matrix}$ $\begin{matrix}{C^{*} = {{g\left( \frac{M_{z}}{M_{w}} \right)} = \left\{ \begin{matrix}0 & {\frac{M_{z}}{M_{w}} < {{2.2}1}} \\{{{0.5}944\ {\ln\left( {\frac{M_{z}}{M_{w}} - {1.5}} \right)}} + {{0.2}057}} & {\frac{M_{z}}{M_{w}} \geq {{2.2}1}}\end{matrix} \right.}} & \left( {{Eq}.3} \right)\end{matrix}$

Similarly, the measured INF values of LCB ethylene interpolymersmeasured at 190° C. at an angular frequency of 0.1 rad/s over a strainamplitude range of 1-10³%, as shown by the solid line in FIG. 4 , can bedescribed using the following formula (INF is dimensionless):

$\begin{matrix}{{{INF} = {{- K}{\zeta^{1.45}\left( {\zeta^{a} - C} \right)}}};{\zeta = {\gamma_{0}{\cos\delta}_{a_{M}\omega}}}} & \left( {{Eq}.4} \right)\end{matrix}$

in which K is a constant equal 0.3722 and γ₀, a_(M) and δ_(a) _(M) _(ω)parameters have the same definition as in Eq.1. Parameters a and C inEq. 4 were used as fitted constants by minimizing sum of squaredresiduals for data point with at least 0.1% nonlinearity (i.e. athird-order harmonic ratio I_(3/1) of at least 0.001) to describedifferent experimental intracycle viscous nonlinear behaviors rangingfrom an intracycle shear-thinning (INF<0) behavior to an intracycleshear-thickening behavior (INF>0).

Based on the above formulations, one can define a parameter purelyreflecting the impact of branching content on the intracycle nonlinearfunction, INF; specifically, a ‘network parameter’, Δ_(int.) can beformulated based on the integrated area between the measured INF andINF^(lin) over an ζ interval of 0.01 to 0.7 as follows:

$\begin{matrix}{\Delta_{{int}.} = {{\int_{{0.0}1}^{0.7}{\left\lbrack {{INF} - {INF}^{lin}} \right\rbrack d\zeta}} = \left\lbrack {{\frac{- K}{a + 2.45}\zeta^{a + 2.45}} + {\frac{KC}{2.45}\zeta^{2.45}} + {\frac{K}{a + 2.45}\zeta^{a^{*} + 2.45}} - {\frac{{KC}^{*}}{2.45}\zeta^{2.45}}} \right\rbrack_{{0.0}1}^{0.7}}} & \left( {{Eq}.5} \right)\end{matrix}$

In fact, the presence of long side branches delays the breakdown of theentanglement network under a strong oscillatory shear-field which couldbe detected using the nonlinear rheology network parameter, Δ_(int.),described above in Eq.4. The network parameter, Δ_(int.), has highsensitivity to the presence of long-chain branched species in ethyleneinterpolymer products. A graphical representation of the intracyclenonlinear function, INF, and the network parameter, Δ_(int.), are shownin FIGS. 3 and 4 . In Table 2, the molecular features as well as thenetwork parameters of the disclosed ethylene interpolymer products, aswell as comparative examples are tabulated.

Comparative examples T1, T2 and T3 were commercially available1-hexene/ethylene interpolymers, specifically Exceed 1018CA, Exceed1012HA, Exceed 1015HA from ExxonMobil Chemical Company, Spring, Tex.Comparative 5a, Comparative 1a, Comparative 4 and Comparative 6 werecommercial 1-octenelethylene copolymers from NOVA Chemicals Corporation,specifically SCLAIR FP120-A, SURPASS FPs117, SURPASS SPs116 and SURPASSFPs016 from NOVA Chemicals Corporation. Comparative Resin 34 was acommercial ethylene homopolymer from NOVA Chemicals Corporation underthe commercial code name of SURPASS HPs167.

The linear Comparatives T1, T2, T3, 1a, 4, 5a, 6 and Resin 34 werecommercial single reactor or dual reactor resins produced in solution orgas phase processes with Ziegler-Natta, homogeneous and mixed(Ziegler-Natta+homogeneous) catalyst formulations and had an

$\frac{M_{z}}{M_{w}}$from about 1.5 to about 3.5. These linear ethyleneinterpolymers/homopolymers had no or undetectable levels of LCB species,i.e. a network parameter Δ_(int.) less than 0.01. The solid linescoplotted with the experimental data points in FIG. 3 are predictedtrends according to the Eq.1-3. As can be seen, a good agreement betweenthe predicted trend and measured intracycle nonlinear function values,INF, of these linear interpolymers (e.g. non-limiting Comparatives T1,T2, T3 and 5a shown in FIG. 3 ) were observed indicating the fact thatthe presented scaling functions in Eq. 1 to 3 can sufficiently describethe effect of MW and MWD in the case of linear ethylene interpolymers.

Long chain branched ethylene interpolymers of Examples 1 and 2 wereethylene interpolymer products produced using a bridged metallocenecatalyst formulation in a first and a second solution polymerizationreactors. Detailed synthesis conditions for the Example 1 and 2 can befound in Tables 4A and 4B. Comparative 3a contains LCB and was producedin the solution pilot plant using a bridged metallocene catalystformulation in the first reactor and an in-line Ziegler-Natta catalystformulation in the second reactor. Example 8 contain LCB and wasproduced in the solution pilot plant employing a bridged metallocenecatalyst formulation in the first reactor and an unbridged metallocenecatalyst formulation in the second reactor.

Example 1 and 2, as summarized in Table 2, showed a network parameter of0.0427 and 0.0468. Similarly, Example 8 and Comparative 3a had networkparameters significantly greater than 0.01 which is indicative of thepresence of LCB points in the microstructure of these compositions;specifically, as tabulated in Table 2, they had network parameter valuesof 0.0545 and 0.0637, respectively. The ζ-dependence of the INF ofExamples 1, 2, 8 and Comparative 3a deviate from the predicted trendbased on the Eq.1-3 due to the presence of long-chain branchedmacromolecules. The intracycle nonlinear function, INF, of thelong-chain branched ethylene interpolymers in Examples 1, 2, 8 andComparative 3a initially showed a zero INF value (linear regime) andthen exhibited a sign change to a positive INF value as a nonlinearresponse developed (e.g. see FIG. 4 ). Noticeably, a positive maximumwas evident for these resins. At larger strain amplitudes the INF valueschange sign to negative values.

Comparatives R1, R2 and R3 were commercial products called AffinityPL1880G, Affinity PL1840G and Affinity 1845 available from The DowChemical Company, Midland Mich. Comparative S1, S2, S3 and S4 werecommercial products called Enable available from ExxonMobil ChemicalCompany, Spring Tex.; specifically Enable 20-05HH, Enable 27-03, Enable35-05CH and Enable 23-05. Comparatives Q1 through Q4 were commercialproducts called Queo available from Borealis, Vienna, Austria;specifically, Comparative Q1 was Queo 0201, Comparative Q2 was Queo8201, Comparative Q3 was Queo 0203 and Comparative Q4 was Queo 1001.Comparatives V2a, V3 and V4 were commercial products coded Elite 5100G,Elite 5500G and Elite 5400G available from the Dow Chemical Company,Midland, Mich. Comparative U1 was a commercial product coded Elite AT6202 available from the Dow Chemical Company, Midland, Mich. As shown inTable 2 Comparatives S1 through S4 contained LCB, having networkparameter values of 0.0755, 0.0785, 0.0751 and 0.0701, respectively.Table 2 further discloses that Comparative U1 contains detectableamounts of LCB; i.e. a network parameter value of 0.0591 which issignificantly greater than 0.01. Similarly, as summarized in Table 2,the Comparatives V2a, V3 and V4 comprise long-chain branched species asnetwork parameter values of 0.0435, 0.0260 and 0.0517 were observed forthese samples. Given Table 2, it was evident that Comparative Q1, Q2, Q3and Q4 contained long-chain branching, i.e. network parameter values of0.0648, 0.0629, 0.0501 and 0.0617, respectively. As can be found inTable 2, Comparatives R1, R2 and R3 had network parameter values of0.0648, 0.0711 and 0.0573.

The ζ-dependence of the INF of Comparatives S1 through S4 and R1 and R2and Comparatives Q1, Q2 and Q4 and Comparatives V2a, V3, V4 and U1deviate from the predicted trend based on the Eq.1-3 due to the presenceof long-chain branched macromolecules. The intracycle nonlinearfunction, INF, of the long-chain branched ethylene interpolymers inthese Comparatives initially showed a zero INF value (linear regime) andthen exhibited a sign change to a positive INF value as a nonlinearresponse developed. Noticeably, a positive maximum was evident for theseresins. At larger strain amplitudes the INF values change sign tonegative values as the polymer melt entered a highly nonlinear regime.Comparatives Q3 and R3 initially displayed a zero INF value (linearregime) and then exhibited a sign change to negative INF values as anonlinear response developed. Noticeably, no positive maximum wasevident for these resins. These lower molecular weight Comparatives haddetectable amounts of LCB and showed a departure from the predictedbase-line trend for linear counterparts as described in Eq.1-3.

In this disclosure the network parameter, Δ_(int.), was used tocharacterize the LCB content in ethylene interpolymer products. Thevariation of the network parameter, Δ_(int.), when plotted against anormalized molecular weight, was an essential feature to differentiatethe ethylene interpolymer products, disclosed herein, from comparativepolyethylenes. In this context, one can plot the network parameter,Δ_(int.), as a function of a normalized molecular weight

$Z = \frac{M_{w}}{M_{e}}$in which M_(w) was the weight average molecular weight and M_(e) was themolecular weigh between entanglements. For calculating M_(e) theequation with a power-law-like dependence on molecular weight perbackbone bond m_(b) proposed by Feters et al. (Macromolecules, 1994, 27,pp 4639-4647) was used for m_(b)s between 14 to 28 g/mol:

$\begin{matrix}{M_{e} = {\frac{4}{5}\frac{\rho RTm_{b}^{3.49}}{24820}}} & \left( {{Eq}\text{.5}} \right)\end{matrix}$

in which m_(b) was the molecular weight per backbone bond. As can beseen m_(b) was a function of comonomer type and content. The parameter Twas the absolute temperature at which Δ_(int.) was measured, ρ was themelt-state density at the temperature Δ_(int.) was measured (i.e. 0.780g/cm³ at 190° C., or 463.15 Kelvin) and R was the universal gas constantwith a value of 8.314 J/(mol·Kelvin). The molecular weight per backbonebond m_(b) was calculated in units of g/mol as defined by Chen et al. inJ. Rheol. 2010, 54, pp 393-406 as follows:

$\begin{matrix}{m_{b} = \frac{{n_{c}M_{w/c}} + {28\left( {1 - n_{c}} \right)}}{2}} & \left( {{Eq}.6} \right)\end{matrix}$

where n_(c) is the comonomer content in mole fraction determined byFourier transform infrared (FTIR) spectroscopy according to ASTMD6645-01 (2001) and M_(w/c) is the molecular weight of the comonomer(e.g. 112.22 g/mol for 1-octene).

The Δ_(int.)−Z plot shown in FIG. 5 differentiates Examples 1, 2 and 8from long chain branched Comparatives R1 through R3, Q1 through Q4, S1through S4, V2a, V3, V4, U1 and 3a, and linear Comparatives 5a, T2 andResin 34, using a polydispersity and molecular-weight independent‘network parameter’, Δ_(int.), characterized by the followinginequalities defined in Eq.7 and Eq.8;

$\begin{matrix}{{{0.0}1 \times \left( {Z - 50} \right)^{{0.7}8}} \leq \Delta_{{int}.} \leq {0.01 \times \left( {Z - {60}} \right)^{{0.7}8}}} & \left( {{Eq}\text{.7}} \right)\end{matrix}$ $\begin{matrix}{\Delta_{{int}.} \geq 0.01} & \left( {{Eq}\text{.8}} \right)\end{matrix}$

again, Z was the normalized molecular weight

$\left( {Z = \frac{M_{w}}{M_{e}}} \right).$As shown in FIG. 5 , the network parameter Δ_(int.) of all the linearComparatives ranges within values less than 0.01, i.e. Comparatives 5a,T2 and Resin 34. The range specified by equations 7 and 8 encompassessingle/multi-component ethylene interpolymer compositions made bydifferent combinations of the unbridged and bridged metallocene catalystformulations with an intermediate Z-value (e.g. 58≤Z≤68 at a Δ_(int.) of0.0506) containing LCB structures in levels leading to an intracycleshear-thickening nonlinear behavior with a Δ_(int.) satisfying Eq.7 and8. In fact, Eq. 7 and 8, specifically within a Z range of 58 to 68,characterize architectures with LCB contents in amounts sufficient tointensify elasticity-related properties (e.g. melt-strength, homogeneousdeformation under extension, etc.) while maintaining a relatively fastself-diffusion rate. These characteristics enable resin compositionsappropriate for processes such as film-blowing with high throughputsduring extrusion, stable deformation under extensional action (e.g.film-blowing, thermoforming, etc.) and fast interphase formation duringheat-sealing process.

Solution Polymerization Process

Embodiments of the continuous solution polymerization process are shownin FIGS. 6 and 7 . FIGS. 6 and 7 are not to be construed as limiting, itbeing understood, that embodiments are not limited to the precisearrangement of, or number of, vessels shown. In brief, FIG. 6illustrates one continuously stirred tank reactor (CSTR) followed by anoptional tubular reactor and FIG. 7 illustrates two CSTRs followed by anoptional tubular reactor. The dotted lines in FIGS. 6 and 7 illustrateoptional features of the continuous polymerization process. In thisdisclosure, equivalent terms for tubular reactor 117 shown in FIG. 7 ,were the ‘third reactor’ or ‘R3’; optionally a third ethyleneinterpolymer was produced in this

reactor. Turning to FIG. 6 that has one CSTR, the terms third reactor orR3 were also used to describe tubular reactor 17; wherein a thirdethylene interpolymer was optionally produced.

In FIG. 6 process solvent 1, ethylene 2 and optional α-olefin 3 arecombined to produce reactor feed stream RF1 which flows into reactor 11a. It is not particularly important that combined reactor feed streamRF1 be formed; i.e. reactor feed streams can be combined in all possiblecombinations, including an embodiment where streams 1 through 3 areindependently injected into reactor 11 a. Optionally hydrogen may beinjected into reactor 11 a through stream 4; hydrogen is generally addedto control the molecular weight of the first ethylene interpolymerproduced in reactor 11 a. Reactor 11 a is continuously stirred bystirring assembly 11 b which includes a motor external to the reactorand an agitator within the reactor.

A bridged metallocene catalyst formulation is injected into reactor 11 avia stream 5 e. Catalyst component streams 5 d, 5 c, 5 b and optional 5a refer to the ionic activator (Component B), the bulky ligand-metalcomplex (Component A), the alumoxane co-catalyst (Component M) andoptional hindered phenol (Component P), respectively. The catalystcomponent streams can be arranged in all possible configurations,including an embodiment where streams 5 a through 5 d are independentlyinjected into reactor 11 a. Each catalyst component is dissolved in acatalyst component solvent. Catalyst component solvents, for ComponentsA, B, M and P may be the same or different. Catalyst component solventsare selected such that the combination of catalyst components does notproduce a precipitate in any process stream; for example, precipitationof a catalyst component in stream 5 e. In this disclosure, the term‘first homogeneous catalyst assembly’ refers the combination of streams5 a through 5 e, flow controllers and tanks (not shown in FIG. 6 ) thatfunctions to deliver the bridged metallocene catalyst formulation to thefirst reactor 11 a. The optimization of the bridged metallocene catalystformulation is described below.

Reactor 11 a produces a first exit stream, stream 11 c, containing thefirst ethylene interpolymer dissolved in process solvent, as well asunreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen(if present), active catalyst, deactivated catalyst, residual catalystcomponents and other impurities (if present).

Optionally the first exit stream, stream 11 c, is deactivated by addinga catalyst deactivator A from catalyst deactivator tank 18A forming adeactivated solution A, stream 12 e; in this case, FIG. 6 defaults to asingle reactor solution process. If a catalyst deactivator is not added,stream 11 c enters tubular reactor reactor 17. Catalyst deactivator A isdiscussed below.

The term “tubular reactor” is meant to convey its conventional meaning,namely a simple tube; wherein the length/diameter (LID) ratio is atleast 10/1. Optionally, one or more of the following reactor feedstreams may be injected into tubular reactor 17; process solvent 13,ethylene 14 and α-olefin 15. As shown in FIG. 6 , streams 13, 14 and 15may be combined forming reactor feed stream RF3 and the latter isinjected into reactor 17. It is not particularly important that streamRF3 be formed; i.e. reactor feed streams can be combined in all possiblecombinations. Optionally hydrogen may be injected into reactor 17through stream 16. Optionally, a homogeneous or a heterogeneous catalystformulation may be injected into reactor 17. Non-limiting examples of ahomogeneous catalyst formulation includes a bridged metallocene catalystformulation, an unbridged single site catalyst formulation, or ahomogeneous catalyst formulation where the bulky ligand-metal complex isnot a member of the genera defined by Formula (I) or Formula (II).Stream 40 in FIG. 6 represents the output from a ‘second homogeneouscatalyst assembly’. One embodiment of the second homogeneous catalystassembly is similar to the first homogeneous catalyst assembly describedabove, i.e. having similar streams, flow controllers and vessels.

In FIG. 6 , streams 34 a through 34 h represent a ‘heterogeneouscatalyst assembly’. In one embodiment an in-line Ziegler-Natta catalystformulation is produced in the heterogeneous catalyst assembly. Thecomponents that comprise the in-line Ziegler-Natta catalyst formulationare introduced through streams 34 a, 34 b, 34 c and 34 d. Stream 34 acontains a blend of an aluminum alkyl and a magnesium compound, stream34 b contains a chloride compound, stream 34 c contains a metal compoundand stream 34 d contains an alkyl aluminum co-catalyst. An efficientin-line Ziegler-Natta catalyst formulation if formed by optimizing thefollowing molar ratios: (aluminum alkyl)/(magnesium compound) or(ix)/(v); (chloride compound)/(magnesium compound) or (vi)/(v); (alkylaluminum co-catalyst)/(metal compound) or (viii)/(vii), and; (aluminumalkyl)/(metal compound) or (ix)/(vii); as well as the time thesecompounds have to react and equilibrate.

Stream 34 a contains a binary blend of a magnesium compound, component(v) and an aluminum alkyl, component (ix), in process solvent. The upperlimit on the (aluminum alkyl)/(magnesium compound) molar ratio in stream10 a may be 70, in some cases 50 and is other cases 30. The lower limiton the (aluminum alkyl)/(magnesium compound) molar ratio may be 3.0, insome cases 5.0 and in other cases 10. Stream 34 b contains a solution ofa chloride compound, component (vi), in process solvent. Stream 34 b iscombined with stream 34 a and the intermixing of streams 34 a and 34 bproduces a magnesium chloride catalyst support. To produce an efficientin-line Ziegler-Natta catalyst (efficient in olefin polymerization), the(chloride compound)/(magnesium compound) molar ratio is optimized. Theupper limit on the (chloride compound)/(magnesium compound) molar ratiomay be 4, in some cases 3.5 and is other cases 3.0. The lower limit onthe (chloride compound)/(magnesium compound) molar ratio may be 1.0, insome cases 1.5 and in other cases 1.9. The time between the addition ofthe chloride compound and the addition of the metal compound (component(vii)) via stream 34 c is controlled; hereafter HUT-1 (the firstHold-Up-Time). HUT-1 is the time for streams 34 a and 34 b toequilibrate and form a magnesium chloride support. The upper limit onHUT-1 may be 70 seconds, in some cases 60 seconds and is other cases 50seconds. The lower limit on HUT-1 may be 5 seconds, in some cases 10seconds and in other cases 20 seconds. HUT-1 is controlled by adjustingthe length of the conduit between stream 34 b injection port and stream34 c injection port, as well as controlling the flow rates of streams 34a and 34 b. The time between the addition of component (vii) and theaddition of the alkyl aluminum co-catalyst, component (viii), via stream34 d is controlled; hereafter HUT-2 (the second Hold-Up-Time). HUT-2 isthe time for the magnesium chloride support and stream 34 c to react andequilibrate. The upper limit on HUT-2 may be 50 seconds, in some casesseconds and is other cases 25 seconds. The lower limit on HUT-2 may be 2seconds, in some cases 6 seconds and in other cases 10 seconds. HUT-2 iscontrolled by adjusting the length of the conduit between stream 34 cinjection port and stream 34 d injection port, as well as controllingthe flow rates of streams 34 a, 34 b and 34 c. The quantity of the alkylaluminum co-catalyst added is optimized to produce an efficientcatalyst; this is accomplished by adjusting the (alkyl aluminumco-catalyst)/(metal compound) molar ratio, or (viii)/(vii) molar ratio.The upper limit on the (alkyl aluminum co-catalyst)/(metal compound)molar ratio may be 10, in some cases 7.5 and is other cases 6.0. Thelower limit on the (alkyl aluminum co-catalyst)/(metal compound) molarratio may be 0, in some cases 1.0 and in other cases 2.0. In addition,the time between the addition of the alkyl aluminum co-catalyst and theinjection of the in-line Ziegler-Natta catalyst formulation into reactor17 is controlled; hereafter HUT-3 (the third Hold-Up-Time). HUT-3 is thetime for stream 34 d to intermix and equilibrate to form the in-lineZiegler Natta catalyst formulation. The upper limit on HUT-3 may be 15seconds, in some cases 10 seconds and is other cases 8 seconds. Thelower limit on HUT-3 may be 0.5 seconds, in some cases 1 seconds and inother cases 2 seconds. HUT-3 is controlled by adjusting the length ofthe conduit between stream 34 d injection port and the catalystinjection port in reactor 17, and by controlling the flow rates ofstreams 34 a through 34 d. As shown in FIG. 6 , optionally, 100% ofstream 34 d, the alkyl aluminum co-catalyst, may be injected directlyinto reactor 17 via stream 34 h. Optionally, a portion of stream 34 dmay be injected directly into reactor 17 via stream 34 h and theremaining portion of stream 34 d injected into reactor 17 via stream 34f.

The quantity of in-line heterogeneous catalyst formulation added toreactor 17 is expressed as the parts-per-million (ppm) of metal compound(component (vii)) in the reactor solution, hereafter “R3 (vii) (ppm)”.The upper limit on R3 (vii) (ppm) may be 10 ppm, in some cases 8 ppm andin other cases 6 ppm. The lower limit on R3 (vii) (ppm) in some casesmay be 0.5 ppm, in other cases 1 ppm and in still other cases 2 ppm. The(aluminum alkyl)/(metal compound) molar ratio in reactor 17, or the(ix)/(vii) molar ratio, is also controlled. The upper limit on the(aluminum alkyl)/(metal compound) molar ratio in the reactor may be 2,in some cases 1.5 and is other cases 1.0. The lower limit on the(aluminum alkyl)/(metal compound) molar ratio may be 0.05, in some cases0.075 and in other cases 0.1.

Any combination of the streams employed to prepare and deliver thein-line Ziegler-Natta catalyst formulation to reactor 17 may be heatedor cooled, i.e. streams 34 a through 34 h; in some cases the uppertemperature limit of streams 34 a through 34 h may be 90° C., in othercases 80° C. and in still other cases 70° C. and; in some cases thelower temperature limit may be 20° C.; in other cases 35° C. and instill other cases 50° C.

In reactor 17 a third ethylene interpolymer may, or may not, form. Athird ethylene interpolymer will not form if catalyst deactivator A isadded upstream of reactor 17 via catalyst deactivator tank 18A. A thirdethylene interpolymer will be formed if catalyst deactivator B is addeddownstream of reactor 17 via catalyst deactivator tank 18B forming adeactivated solution, i.e. stream 19.

The optional third ethylene interpolymer produced in reactor 17 may beformed using a variety of operational modes; with the proviso thatcatalyst deactivator A is not added upstream of reactor 17. Non-limitingexamples of operational modes include: (a) residual ethylene, residualoptional α-olefin and residual active catalyst entering reactor 17 reactto form the optional third ethylene interpolymer, or; (b) fresh processsolvent 13, fresh ethylene 14 and optional fresh α-olefin 15 are addedto reactor 17 and the residual active catalyst entering reactor 17 formsthe optional third ethylene interpolymer, or; (c) a fresh catalystformulation is added to reactor 17 to polymerize residual ethylene andresidual optional α-olefin to form the optional third ethyleneinterpolymer, or; (d) fresh process solvent 13, ethylene 14, optionalα-olefin 15 and a fresh catalyst formulation are added to reactor 17 toform the optional third ethylene interpolymer.

In FIG. 6 , deactivated solution A (stream 12 e) or B (stream 19) passesthrough pressure let down device 20 and heat exchanger 21. If theoptional heterogeneous catalyst formulation has been added, a passivatormay be added via tank 22 forming a passivated solution 23. Thepassivated solution, deactivated solution A or deactivated solution Bpasses through pressure let down device 24 and enters a firstvapor/liquid separator 25; hereinafter, “V/L” is equivalent tovapor/liquid. Two streams are formed in the first V/L separator a firstbottom stream 27 comprising a solution that is ethylene interpolymerrich and also contains residual ethylene, residual optional α-olefinsand catalyst residues, and; a first gaseous overhead stream 26comprising ethylene, process solvent, optional α-olefins, optionalhydrogen, oligomers and light-end impurities if present.

The first bottom stream enters a second V/L separator 28. In the secondV/L separator two streams are formed: a second bottom stream 30comprising a solution that is richer in ethylene interpolymer productand leaner in process solvent relative to the first bottom stream 27,and; a second gaseous overhead stream 29 comprising process solvent,optional α-olefins, ethylene, oligomers and light-end impurities ifpresent.

The second bottom stream 30 flows into a third V/L separator 31. In thethird V/L separator two streams are formed: a product stream 33comprising an ethylene interpolymer product, deactivated catalystresidues and less than 5 weight % of residual process solvent, and; athird gaseous overhead stream 32 comprised essentially of processsolvent, optional α-olefins and light-end impurities if present.

Embodiments also include the use of one or more V/L separators operatingat reduced pressure, i.e. the operating pressure is lower thanatmospheric pressure and/or embodiments where heat is added during thedevolitization process, i.e. one or more heat exchangers are employedupstream of, or within, one or more of the V/L separators. Suchembodiments facilitate the removal of residual process solvent andcomonomer such that the residual volatiles in ethylene interpolymerproducts are less than 500 ppm.

Product stream 33 proceeds to polymer recovery operations. Non-limitingexamples of polymer recovery operations include one or more gear pump,single screw extruder or twin screw extruder that forces the moltenethylene interpolymer product through a pelletizer. Other embodimentsinclude the use of a devolatilizing extruder, where residual processsolvent and optional α-olefin may be removed such that the volatiles inthe ethylene interpolymer product is less than 500 ppm. Once pelletizedthe solidified ethylene interpolymer product is typically transported toa product silo.

The first, second and third gaseous overhead streams shown in FIG. 6(streams 26, 29 and 32, respectively) are sent to a distillation columnwhere solvent, ethylene and optional α-olefin are separated forrecycling, or; the first, second and third gaseous overhead streams arerecycled to the reactors, or; a portion of the first, second and thirdgaseous overhead streams are recycled to the reactors and the remainingportion is sent to a distillation column.

FIG. 7 illustrates an embodiment of the continuous solutionpolymerization process employing two CSTR reactors and an optionaltubular reactor. Process solvent 101, ethylene 102 and optional α-olefin103 are combined to produce reactor feed stream RF101 which flows intoreactor 111 a. Optionally hydrogen may be injected into reactor 111 athrough stream 104. Reactor 111 a is continuously stirred by stirringassembly 111 b.

A first bridged metallocene catalyst formulation is injected intoreactor 111 a via stream 105 e. Catalyst component streams 105 d, 105 c,105 b and optional 105 a contain the ionic activator (Component B¹,where the superscript ‘¹’ denotes the first reactor), the bulkyligand-metal complex (Component A¹), the alumoxane co-catalyst(Component M¹) and optional hindered phenol (Component P¹),respectively. Each catalyst component is dissolved in a catalystcomponent solvent. Catalyst component solvents, for Components A₁, B¹,M¹ and P¹ may be the same or different. In FIG. 7 , the firsthomogeneous catalyst assembly refers the combination of streams 105 athrough 105 e, flow controllers and tanks that functions to deliver theactive bridged metallocene catalyst formulation to reactor 111 a.

Reactor 111 a produces a first exit stream, stream 111 c, containing thefirst ethylene interpolymer dissolved in process solvent. FIG. 7includes two embodiments where reactors 111 a and 112 a can be operatedin series or parallel modes. In series mode 100% of stream 111 c (thefirst exit stream) passes through flow controller 111 d forming stream111 e which enters reactor 112 a. In contrast, in parallel mode 100% ofstream 111 c passes through flow controller 111 f forming stream 111 g.Stream 111 g by-passes reactor 112 a and is combined with stream 112 c(the second exit stream) forming stream 112 d (the third exit stream).

Fresh reactor feed streams are injected into reactor 112 a; processsolvent 106, ethylene 107 and optional α-olefin 108 are combined toproduce reactor feed stream RF102. It is not important that stream RF102is formed; i.e. reactor feed streams can be combined in all possiblecombinations, including independently injecting each stream into thereactor. Optionally hydrogen may be injected into reactor 112 a throughstream 109 to control the molecular weight of the second ethyleneinterpolymer. Reactor 112 a is continuously stirred by stirring assembly112 b which includes a motor external to the reactor and an agitatorwithin the reactor.

As shown in FIG. 7 , a second bridged metallocene catalyst formulationis injected into reactor 112 a through stream 110 e and a secondethylene interpolymer is formed in reactor 112 a. Catalyst componentstreams 110 d, 110 c, 110 b and 110 a contain the ionic activatorComponent B² (where the superscript ‘²’ denotes the second reactor), thebulky ligand-metal complex (Component A²), the alumoxane co-catalyst(Component M²) and optional hindered phenol (Component P²),respectively. The catalyst component streams can be arranged in allpossible configurations, including an embodiment where streams 110 athrough 110 d are independently injected into reactor 111 a. Eachcatalyst component is dissolved in a catalyst component solvent.

Formula (I) defines the genus of catalyst Component A; however,Component A² employed in reactor 112 a may be the same, or different,relative to catalyst Component A¹ employed in reactor 111 a. Similarly,the chemical composition of catalyst Components B² and B¹, catalystComponents M² and M¹ and catalysts Component P² and P¹ may be the same,or different. In this disclosure, the term ‘second homogeneous catalystassembly’ refers the combination of streams 110 a through 110 e, flowcontrollers and tanks that functions to deliver the second bridgedmetallocene catalyst formulation to the second reactor, reactor 112 a inFIG. 7 . The optimization of the first and second bridged metallocenecatalyst formulation is described below.

Although not shown in FIG. 7 , an additional embodiment includes thesplitting of stream 105 a into two streams, such that a portion of steam105 a is injected into reactor 111 a and the remaining portion of stream105 a is injected into reactor 112 a. In other words, the first bridgedmetallocene catalyst formulation is injected into both reactors.

If reactors 111 a and 112 a are operated in a series mode, the secondexit stream 112 c contains the second ethylene interpolymer and thefirst ethylene interpolymer dissolved in process solvent; as well asunreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen(if present), active catalysts, deactivated catalysts, catalystcomponents and other impurities (if present). Optionally the second exitstream 112 c is deactivated by adding a catalyst deactivator A fromcatalyst deactivator tank 118A forming a deactivated solution A, stream112 e; in this case, FIG. 7 defaults to a dual reactor solution process.If the second exit stream 112 c is not deactivated the second exitstream enters tubular reactor 117.

If reactors 111 a and 112 a are operated in parallel mode, the secondexit stream 112 c contains the second ethylene interpolymer dissolved inprocess solvent. The second exit stream 112 c is combined with stream111 g forming a third exit stream 112 d, the latter contains the secondethylene interpolymer and the first ethylene interpolymer dissolved inprocess solvent. Optionally the third exit stream 112 d is deactivatedby adding catalyst deactivator A from catalyst deactivator tank 118Aforming deactivated solution A, stream 112 e. If the third exit stream112 d is not deactivated the third exit stream 112 d enters tubularreactor 117.

Optionally, one or more of the following reactor feed streams may beinjected into tubular reactor 117; process solvent 113, ethylene 114 andα-olefin 115. As shown in FIG. 7 , streams 113, 114 and 115 may becombined forming reactor feed stream RF103 and injected into reactor117. It is not particularly important that stream RF103 be formed; i.e.reactor feed streams can be combined in all possible combinations.Optionally hydrogen may be injected into reactor 117 through stream 116.

Optionally, a homogeneous or a heterogeneous catalyst formulation may beinjected into reactor 117. Non-limiting examples of a homogeneouscatalyst formulation includes a bridged metallocene catalystformulation, an unbridged single site catalyst formulation, or ahomogeneous catalyst formulation where the bulky ligand-metal complex isnot a member of the genera defined by Formula (I) or Formula (II).Stream 140 in FIG. 7 represents the output from a ‘third homogeneouscatalyst assembly’. One embodiment of the third homogeneous catalystassembly is similar to the first homogeneous catalyst assembly describedabove, i.e. having similar streams, flow controllers and vessels.

In FIG. 7 , streams 134 a through 134 h represent a ‘heterogeneouscatalyst assembly’. In one embodiment an in-line Ziegler-Natta catalystformulation is produced in the heterogeneous catalyst assembly. Thecomponents that comprise the in-line Ziegler-Natta catalyst formulationare introduced through streams 134 a, 134 b, 134 c and 134 d. Stream 134a contains a blend of an aluminum alkyl and a magnesium compound, stream134 b contains a chloride compound, stream 134 c contains a metalcompound and stream 134 d contains an alkyl aluminum co-catalyst. Theoptimization of an in-line Ziegler-Natta catalyst formulation isdescribed above.

Once prepared, the in-line Ziegler-Natta catalyst is injected intoreactor 117 through stream 134 e; optionally, additional alkyl aluminumco-catalyst is injected into reactor 117 through stream 134 h. As shownin FIG. 7 , optionally, 100% of stream 134 d, the alkyl aluminumco-catalyst, may be injected directly into reactor 117 via stream 134 h.Optionally, a portion of the alkyl aluminum co-catalyst may be injecteddirectly into reactor 117 via stream 134 h and the remaining portioninjected into reactor 117 via stream 134 e. Any combination of thestreams that comprise the heterogeneous catalyst assembly may be heatedor cooled, i.e. streams 134 a-134 e and 134 h.

A third ethylene interpolymer may, or may not, form in reactor 117. Athird ethylene interpolymer will not form if catalyst deactivator A isadded upstream of reactor 117 via catalyst deactivator tank 118A. Athird ethylene interpolymer will be formed if catalyst deactivator B isadded downstream of reactor 117 via catalyst deactivator tank 118B. Theoptional third ethylene interpolymer produced in reactor 117 may beformed using a variety of operational modes, as described above; withthe proviso that catalyst deactivator A is not added upstream of reactor17.

In series mode, Reactor 117 produces a third exit stream 117 bcontaining the first ethylene interpolymer, the second ethyleneinterpolymer and optionally a third ethylene interpolymer. As shown inFIG. 7 , catalyst deactivator B may be added to the third exit stream117 b via catalyst deactivator tank 118B producing a deactivatedsolution B, stream 119; with the proviso that catalyst deactivator B isnot added if catalyst deactivator A was added upstream of reactor 117.As discussed above, if catalyst deactivator A was added, deactivatedsolution A (stream 112 e) is equivalent to stream 117 b that exitstubular reactor 117.

In parallel mode, reactor 117 produces a fourth exit stream 117 bcontaining the first ethylene interpolymer, the second ethyleneinterpolymer and optionally a third ethylene interpolymer (as discussedabove, in parallel mode, stream 112 d is the third exit stream). Asshown in FIG. 7 , in parallel mode, catalyst deactivator B is added tothe fourth exit stream 117 b via catalyst deactivator tank 118Bproducing a deactivated solution B, stream 119; with the proviso thatcatalyst deactivator B is not added if catalyst deactivator A was addedupstream of reactor 117.

In FIG. 7 , deactivated solution A (stream 112 e) or B (stream 119)passes through pressure let down device 120 and heat exchanger 121.Optionally, if a heterogeneous catalyst formulation has been added, apassivator may be added via tank 122 forming a passivated solution 123.

Deactivated solution A, deactivated solution B or passivated solution123 pass through pressure let down device 124 and enter a first V/Lseparator 125. Two streams are formed in the first V/L separator a firstbottom stream 127 comprising a solution that is rich in ethyleneinterpolymers, and; a first gaseous overhead stream 126 rich inethylene, solvent, optional α-olefins and optional hydrogen.

The first bottom stream enters a second V/L separator 128. In the secondV/L separator two streams are formed: a second bottom stream 130comprising a solution that is richer in ethylene interpolymer and leanerin process solvent relative to the first bottom stream 127, and; asecond gaseous overhead stream 129.

The second bottom stream 130 flows into a third V/L separator 131. Inthe third V/L separator two streams are formed: a product stream 133comprising an ethylene interpolymer product, deactivated catalystresidues and less than 5 weight % of residual process solvent, and; athird gaseous overhead stream 132. Product stream 133 proceeds topolymer recovery operations.

Other embodiments include the use of one or more V/L separatorsoperating at reduced pressure, i.e. the operating pressure is lower thanatmospheric pressure and/or embodiments where heat is added during thedevolitization process, i.e. one or more heat exchangers are employedupstream of, or within, one or more of the V/L separators. Suchembodiments facilitate the removal of residual process solvent andcomonomer such that the residual volatiles in ethylene interpolymerproducts are less than 500 ppm.

Product stream 133 proceeds to polymer recovery operations. Non-limitingexamples of polymer recovery operations include one or more gear pump,single screw extruder or twin screw extruder that forces the moltenethylene interpolymer product through a pelletizer. Other embodimentsinclude the use of a devolatilizing extruder, where residual processsolvent and optional α-olefin may be removed such that the volatiles inthe ethylene interpolymer product is less than 500 ppm. Once pelletizedthe solidified ethylene interpolymer product is typically transported toa product silo.

A highly active bridged metallocene catalyst formulation was produced byoptimizing the proportion of each of the four catalyst components:Component A, Component M, Component B and Component P. The term “highlyactive” means the catalyst formulation is very efficient in convertingolefins to polyolefins. In practice the optimization objective is tomaximize the following ratio: (pounds of ethylene interpolymer productproduced) per (pounds of catalyst consumed). In the case of a singleCSTR, the quantity of the bulky ligand-metal complex, Component A, addedto reactor R1 was expressed as the parts per million (ppm) of ComponentA in the total mass of the solution in R1, i.e. “R1 catalyst (ppm)” asrecited in Table 4A. The upper limit on the ppm of Component A may be 5,in some cases 3 and is other cases 2. The lower limit on the ppm ofComponent A may be 0.02, in some cases 0.05 and in other cases 0.1. Inthe case of two CSTRs, the quantity of Component A added to R1 and R2was controlled and expressed as the parts per million (ppm) of ComponentA in R1 and R2, optionally the quantity of Component A added to R3 wascontrolled and expressed as the parts per million (ppm) of Component Ain R3.

The proportion of Catalyst component B, the ionic activator, added to R1was optimized by controlling the (ionic activator)/(Component A) molarratio, ([B]/[A]), in the R1 solution. The upper limit on the R1 ([B][A])may be 10, in some cases 5 and in other cases 2. The lower limit on R1([B]/[A]) may be 0.3, in some cases 0.5 and in other cases 1.0. Theproportion of catalyst Component M was optimized by controlling the(alumoxane)/(Component A) molar ratio, ([M]/[A]), in the R1 solution.

The alumoxane co-catalyst was generally added in a molar excess relativeto Component A. The upper limit on R1 ([M]/[A]), may be 300, in somecases 200 and is other cases 100. The lower limit on R1 ([M]/[A]), maybe 1, in some cases 10 and in other cases 30. The addition of catalystComponent P (the hindered phenol) to R1 is optional. If added, theproportion of Component P was optimized by controlling the (hinderedphenol)/(alumoxane), ([P]/[M]), molar ratio in R1. The upper limit on R1([P]/[M]) may be 1, in some cases 0.75 and in other cases 0.5. The lowerlimit on R1 ([P]/[M]) may be 0.0, in some cases 0.1 and in other cases0.2.

In embodiments employing two CSTR's and two homogeneous catalystassemblies a second bridged metallocene catalyst formulation may beprepared independently of the first bridged metallocene catalystformulation and optimized as described above. Optionally, a bridgedmetallocene catalyst formulation may be employed in the tubular reactorand optimized as described above.

In the continuous solution processes embodiments shown in FIGS. 6 and 7a variety of solvents may be used as the process solvent; non-limitingexamples include linear, branched or cyclic C₅ to C₁₂ alkanes.Non-limiting examples of α-olefins include 1-propene, 1-butene,1-pentene, 1-hexene, 1-octene, 1-nonene and 1-decene. Suitable catalystcomponent solvents include aliphatic and aromatic hydrocarbons.Non-limiting examples of aliphatic catalyst component solvents includelinear, branched or cyclic C₅₋₁₂ aliphatic hydrocarbons, e.g. pentane,methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane,hydrogenated naphtha or combinations thereof. Non-limiting examples ofaromatic catalyst component solvents include benzene, toluene(methylbenzene), ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene(1,3-dimethylbenzene), p-xylene (1,4-dimethylbenzene), mixtures ofxylene isomers, hemellitene (1,2,3-trimethylbenzene), pseudocumene(1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), mixturesof trimethylbenzene isomers, prehenitene (1,2,3,4-tetramethylbenzene),durene (1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzeneisomers, pentamethylbenzene, hexamethylbenzene and combinations thereof.

It is well known to individuals experienced in the art that reactor feedstreams (solvent, monomer, α-olefin, hydrogen, catalyst formulationetc.) must be essentially free of catalyst deactivating poisons;non-limiting examples of poisons include trace amounts of oxygenatessuch as water, fatty acids, alcohols, ketones and aldehydes. Suchpoisons are removed from reactor feed streams using standardpurification practices; non-limiting examples include molecular sievebeds, alumina beds and oxygen removal catalysts for the purification ofsolvents, ethylene and α-olefins, etc.

Referring to the first reactor shown in FIG. 6 , or the first and secondreactors shown in FIG. 7 , any combination of the feed streams may beheated or cooled: more specifically, streams 1-4 in FIG. 6 and streams101-104 and 106-109 in FIG. 7 . The upper limit on reactor feed streamtemperatures may be 90° C.; in other cases 80° C. and in still othercases 70° C. The lower limit on reactor feed stream temperatures may be20° C.; in other cases, 35° C. and in still other cases 50° C.

Any combination of the streams feeding the tubular reactor may be heatedor cooled; for example, streams 13-16 in FIG. 6 . In some cases, tubularreactor feed streams are tempered, i.e. the tubular reactor feed streamsare heated to at least above ambient temperature. The upper temperaturelimit on the tubular reactor feed streams in some cases are 200° C., inother cases 170° C. and in still other cases 140° C.; the lowertemperature limit on the tubular reactor feed streams in some cases are60° C., in other cases 90° C. and in still other cases 120° C.; with theproviso that the temperature of the tubular reactor feed streams arelower than the temperature of the process stream that enters the tubularreactor.

The operating temperature of the solution polymerization reactors, e.g.vessels 111 a (R1) and 112 a (R2)) in FIG. 7 can vary over a wide range.For example, the upper limit on reactor temperatures in some cases maybe 300° C., in other cases 280° C. and in still other cases 260° C.; andthe lower limit in some cases may be 80° C., in other cases 100° C. andin still other cases 125° C. The second reactor, reactor 112 a (R2), isoperated at a higher temperature than the first reactor 111 a (R1). Themaximum temperature difference between these two reactors(T^(R2)−T^(R1)) in some cases is 120° C., in other cases 100° C. and instill other cases 80° C.; the minimum (T^(R2)−T^(R1)) in some cases is1° C., in other cases 5° C. and in still other cases 10° C. The optionaltubular reactor, reactor 117 (R3), may be operated in some cases 100° C.higher than R2; in other cases 60° C. higher than R2, in still othercases 10° C. higher than R2 and in alternative cases 0° C. higher, i.e.the same temperature as R2. The temperature within optional R3 mayincrease along its length. The maximum temperature difference betweenthe inlet and outlet of R3 in some cases is 100° C., in other cases 60°C. and in still other cases 40° C. The minimum temperature differencebetween the inlet and outlet of R3 is in some cases may be 0° C., inother cases 3° C. and in still other cases 10° C. In some cases, R3 isoperated an adiabatic fashion and in other cases R3 is heated.

The pressure in the polymerization reactors should be high enough tomaintain the polymerization solution as a single phase solution and toprovide the upstream pressure to force the polymer solution from thereactors through a heat exchanger and on to polymer recovery operations.Referring to the embodiments shown in FIGS. 6 and 7 , the operatingpressure of the solution polymerization reactors can vary over a widerange. For example, the upper limit on reactor pressure in some casesmay be 45 MPag, in other cases 30 MPag and in still other cases 20 MPag;and the lower limit in some cases may be 3 MPag, in other some cases 5MPag and in still other cases 7 MPag.

Referring to the embodiments shown in FIGS. 6 and 7 , prior to enteringthe first V/L separator, deactivated solution A, deactivated solution Bor the passivated solution may have a maximum temperature in some casesof 300° C., in other cases 290° C. and in still other cases 280° C.; theminimum temperature may be in some cases 150° C., in other cases 200° C.and in still other cases 220° C. Immediately prior to entering the firstV/L separator, deactivated solution A, deactivated solution B or thepassivated solution in some cases may have a maximum pressure of 40MPag, in other cases 25 MPag and in still cases 15 MPag; the minimumpressure in some cases may be 1.5 MPag, in other cases 5 MPag and instill other cases 6 MPag.

The first V/L separator (vessels 25 and 125 in FIGS. 6 and 7 ,respectively) may be operated over a relatively broad range oftemperatures and pressures. For example, the maximum operatingtemperature of the first V/L separator in some cases may be 300° C., inother cases 285° C. and in still other cases 270° C.; the minimumoperating temperature in some cases may be 100° C., in other cases 140°C. and in still other cases 170° C. The maximum operating pressure ofthe first V/L separator in some cases may be 20 MPag, in other cases 10MPag and in still other cases 5 MPag; the minimum operating pressure insome cases may be 1 MPag, in other cases 2 MPag and in still other cases3 MPag.

The second V/L separator may be operated over a relatively broad rangeof temperatures and pressures. For example, the maximum operatingtemperature of the second V/L separator in some cases may be 300° C., inother cases 250° C. and in still other cases 200° C.; the minimumoperating temperature in some cases may be 100° C., in other cases 125°C. and in still other cases 150° C. The maximum operating pressure ofthe second V/L separator in some cases may be 1000 kPag, in other cases900 kPag and in still other cases 800 kPag; the minimum operatingpressure in some cases may be 10 kPag, in other cases 20 kPag and instill other cases 30 kPag.

The third V/L separator (vessels 31 and 131 in FIGS. 6 and 7 ,respectively) may be operated over a relatively broad range oftemperatures and pressures. For example, the maximum operatingtemperature of the third V/L separator in some cases may be 300° C., inother cases 250° C., and in still other cases 200° C.; the minimumoperating temperature in some cases may be 100° C., in other cases 125°C. and in still other cases 150° C. The maximum operating pressure ofthe third V/L separator in some cases may be 500 kPag, in other cases150 kPag and in still other cases 100 kPag; the minimum operatingpressure in some cases may be 1 kPag, in other cases 10 kPag and instill other cases 25 kPag.

Embodiments of the continuous solution polymerization process shown inFIGS. 6 and 7 show three V/L separators. However, continuous solutionpolymerization embodiments may include configurations comprising atleast one V/L separator.

The ethylene interpolymer product produced in the continuous solutionpolymerization process may be recovered using conventionaldevolatilization systems that are well known to persons skilled in theart, non-limiting examples include flash devolatilization systems anddevolatilizing extruders.

Any reactor shape or design may be used for reactor 111 a (R1) andreactor 112 a (R2) in FIG. 7 ; non-limiting examples include unstirredor stirred spherical, cylindrical or tank-like vessels, as well astubular reactors or recirculating loop reactors. At commercial scale themaximum volume of R1 in some cases may be about 20,000 gallons (about75,710 L), in other cases about 10,000 gallons (about 37,850 L) and instill other cases about 5,000 gallons (about 18,930 L). At commercialscale the minimum volume of R1 in some cases may be about 100 gallons(about 379 L), in other cases about 500 gallons (about 1,893 L) and instill other cases about 1,000 gallons (about 3,785 L). At pilot plantscales reactor volumes are typically much smaller, for example thevolume of R1 at pilot scale could be less than about 2 gallons (lessthan about 7.6 L). In this disclosure the volume of reactor R2 isexpressed as a percent of the volume of reactor R1. The upper limit onthe volume of R2 in some cases may be about 600% of R1, in other casesabout 400% of R1 and in still other cases about 200% of R1. For clarity,if the volume of R1 is 5,000 gallons and R2 is 200% the volume of R1,then R2 has a volume of 10,000 gallons. The lower limit on the volume ofR2 in some cases may be about 50% of R1, in other cases about 100% of R1and in still other cases about 150% of R1. In the case of continuouslystirred tank reactors the stirring rate can vary over a wide range; insome cases from about 10 rpm to about 2000 rpm, in other cases fromabout 100 to about 1500 rpm and in still other cases from about 200 toabout 1300 rpm. In this disclosure the volume of R3, the tubularreactor, is expressed as a percent of the volume of reactor R2. Theupper limit on the volume of R3 in some cases may be about 500% of R2,in other cases about 300% of R2 and in still other cases about 100% ofR2. The lower limit on the volume of R3 in some cases may be about 3% ofR2, in other cases about 10% of R2 and in still other cases about 50% ofR2.

The “average reactor residence time”, a commonly used parameter in thechemical engineering art, is defined by the first moment of the reactorresidence time distribution; the reactor residence time distribution isa probability distribution function that describes the amount of timethat a fluid element spends inside the reactor. The average reactorresidence time can vary widely depending on process flow rates andreactor mixing, design and capacity. The upper limit on the averagereactor residence time of the solution in R1 in some cases may be 600seconds, in other cases 360 seconds and in still other cases 180seconds. The lower limit on the average reactor residence time of thesolution in R1 in some cases may be 10 seconds, in other cases 20seconds and in still other cases 40 seconds. The upper limit on theaverage reactor residence time of the solution in R2 in some cases maybe 720 seconds, in other cases 480 seconds and in still other cases 240seconds. The lower limit on the average reactor residence time of thesolution in R2 in some cases may be 10 seconds, in other cases 30seconds and in still other cases 60 seconds. The upper limit on theaverage reactor residence time of the solution in R3 in some cases maybe 600 seconds, in other cases 360 seconds and in still other cases 180seconds. The lower limit on the average reactor residence time of thesolution in R3 in some cases may be 1 second, in other cases 5 secondsand in still other cases 10 seconds.

Optionally, additional reactors (e.g. CSTRs, loops or tubes, etc.) couldbe added to the continuous solution polymerization process embodimentsshown in FIG. 7 . In this disclosure, the number of reactors is notparticularly important; with the proviso that the continuous solutionpolymerization process comprises at least one reactor that employs atleast one bridged metallocene catalyst formulation.

In operating the continuous solution polymerization process embodimentsshown in FIG. 7 the total amount of ethylene supplied to the process canbe portioned or split between the three reactors R1, R2 and R3. Thisoperational variable is referred to as the Ethylene Split (ES), i.e.“ES^(R1)”, “ES^(R2)” and “ES^(R3)” refer to the weight percent ofethylene injected in R1, R2 and R3, respectively; with the proviso thatES^(R1)+ES^(R2)+ES^(R3)=100%. This is accomplished by adjusting theethylene flow rates in the following streams: stream 102 (R1), stream107 (R2) and stream 114 (R3). The upper limit on ES^(R1) in some casesis about 60%, in other cases about 55% and in still other cases about50%; the lower limit on ES^(R1) in some cases is about 10%, in othercases about 15% and in still other cases about 20%. The upper limit onES^(R2) in some cases is about 90%, in other cases about 80% and instill other cases about 70%; the lower limit on ES^(R2) in some cases isabout 20%, in other cases about 30% and in still other cases about 40%.The upper limit on ES^(R3) in some cases is about 30%, in other casesabout 25% and in still other cases about 20%; the lower limit on ES^(R3)in some cases is 0%, in other cases about 5% and in still other casesabout 10%.

In operating the continuous solution polymerization process embodimentsshown in FIG. 7 the ethylene concentration in each reactor is alsocontrolled. The ethylene concentration in reactor 1, hereafter EC^(R1),is defined as the weight of ethylene in reactor 1 divided by the totalweight of everything added to reactor 1; EC^(R2) and EC^(R3) are definedsimilarly. Ethylene concentrations in the reactors (EC^(R1) or EC^(R2)or EC^(R3)) in some cases may vary from about 7 weight percent (wt. %)to about 25 wt. %, in other cases from about 8 wt. % to about 20 wt. %and in still other cases from about 9 wt. % to about 17 wt. %.

In operating the continuous solution polymerization process embodimentsshown in FIG. 7 the total amount of ethylene converted in each reactoris monitored. The term “Q^(R1)” refers to the percent of the ethyleneadded to R1 that is converted into an ethylene interpolymer by thecatalyst formulation. Similarly, Q^(R2) and Q^(R3) represent the percentof the ethylene added to R2 and R3 that was converted into ethyleneinterpolymer, in the respective reactor. Ethylene conversions can varysignificantly depending on a variety of process conditions, e.g.catalyst concentration, catalyst formulation, impurities and poisons.The upper limit on both Q^(R1) and Q^(R2) in some cases is about 99%, inother cases about 95% and in still other cases about 90%; the lowerlimit on both Q^(R1) and Q^(R2) in some cases is about 65%, in othercases about 70% and in still other cases about 75%. The upper limit onQ^(R3) in some cases is about 99%, in other cases about 95% and in stillother cases about 90%; the lower limit on Q^(R3) in some cases is 0%, inother cases about 5% and in still other cases about 10%. The term“Q^(T)” represents the total or overall ethylene conversion across theentire continuous solution polymerization plant; i.e. Q^(T)=100×[weightof ethylene in the interpolymer product]/([weight of ethylene in theinterpolymer product]+[weight of unreacted ethylene]). The upper limiton Q^(T) in some cases is about 99%, in other cases about 95% and instill other cases about 90%; the lower limit on Q^(T) in some cases isabout 75%, in other cases about 80% and in still other cases about 85%.

Referring to FIG. 7 , optionally, α-olefin may be added to thecontinuous solution polymerization process. If added, α-olefin may beproportioned or split between R1, R2 and R3. This operational variableis referred to as the Comonomer (α-olefin) Split (CS), i.e. “CS^(R1)”,“CS^(R2)” and “CS^(R3)” refer to the weight percent of α-olefincomonomer that is injected in R1, R2 and R3, respectively; with theproviso that CS^(R1)+CS^(R2)+CS^(R3)=100%. This is accomplished byadjusting α-olefin flow rates in the following streams: stream 103 (R1),stream 108 (R2) and stream 115 (R3). The upper limit on CS^(R1) in somecases is 100% (i.e. 100% of the α-olefin is injected into R1), in othercases about 95% and in still other cases about 90%. The lower limit onCS^(R1) in some cases is 0% (ethylene homopolymer produced in R1), inother cases about 5% and in still other cases about 10%. The upper limiton CS^(R2) in some cases is about 100% (i.e. 100% of the α-olefin isinjected into reactor 2), in other cases about 95% and in still othercases about 90%. The lower limit on CS^(R2) in some cases is 0%, inother cases about 5% and in still other cases about 10%. The upper limiton CS^(R3) in some cases is 100%, in other cases about 95% and in stillother cases about 90%. The lower limit on CS^(R3) in some cases is 0%,in other cases about 5% and in still other cases about 10%.

In the continuous polymerization processes described in this disclosure,polymerization is terminated by adding a catalyst deactivator.Embodiments in FIG. 6 show catalyst deactivation occurring either (a)upstream of the tubular reactor by adding a catalyst deactivator A fromcatalyst deactivator tank 18A, or; (b) downstream of the tubular reactorby adding a catalyst deactivator B from catalyst deactivator tank 18B.Catalyst deactivator tanks 18A and 18B may contain neat (100%) catalystdeactivator, a solution of catalyst deactivator in a solvent, or aslurry of catalyst deactivator in a solvent. The chemical composition ofcatalyst deactivator A and B may be the same, or different. Non-limitingexamples of suitable solvents include linear or branched C₅ to C₁₂alkanes. In this disclosure, how the catalyst deactivator is added isnot particularly important. Once added, the catalyst deactivatorsubstantially stops the polymerization reaction by changing activecatalyst species to inactive forms. Suitable deactivators are well knownin the art, non-limiting examples include: amines (e.g. U.S. Pat. No.4,803,259 to Zboril et al.); alkali or alkaline earth metal salts ofcarboxylic acid (e.g. U.S. Pat. No. 4,105,609 to Machan et al.); water(e.g. U.S. Pat. No. 4,731,438 to Bernier et al.); hydrotalcites,alcohols and carboxylic acids (e.g. U.S. Pat. No. 4,379,882 to Miyata);or a combination thereof (U.S. Pat. No. 6,180,730 to Sibtain et al.). Inthis disclosure the quantify of catalyst deactivator added wasdetermined by the following catalyst deactivator molar ratio:0.3≤(catalyst deactivator)/((total catalytic metal)+(alkyl aluminumco-catalyst)+(aluminum alkyl))≤2.0; where the total catalytic metal isthe total moles of catalytic metal added to the solution process. Theupper limit on the catalyst deactivator molar ratio may be 2, in somecases 1.5 and in other cases 0.75. The lower limit on the catalystdeactivator molar ratio may be 0.3, in some cases 0.35 and in stillother cases 0.4. In general, the catalyst deactivator is added in aminimal amount such that the catalyst is deactivated and thepolymerization reaction is quenched.

If the optional heterogeneous catalyst formulation was employed in thethird reactor, prior to entering the first V/L separator, a passivatoror acid scavenger was added to deactivated solution A or B to form apassivated solution, i.e. passivated solution stream 23 as shown in FIG.6 . Optional passivator tank 22 may contain neat (100%) passivator, asolution of passivator in a solvent, or a slurry of passivator in asolvent. Non-limiting examples of suitable solvents include linear orbranched C₅ to C₁₂ alkanes. In this disclosure, how the passivator isadded is not particularly important. Suitable passivators are well knownin the art, non-limiting examples include alkali or alkaline earth metalsalts of carboxylic acids or hydrotalcites. The quantity of passivatoradded can vary over a wide range. The quantity of passivator added wasdetermined by the total moles of chloride compounds added to thesolution process, i.e. the chloride compound “compound (vi)” plus themetal compound “compound (vii)” that was used to manufacture theheterogeneous catalyst formulation. The upper limit on the(passivator)/(total chlorides) molar ratio may be 15, in some cases 13and in other cases 11. The lower limit on the (passivator)/(totalchlorides) molar ratio may be about 5, in some cases about 7 and instill other cases about 9. In general, the passivator is added in theminimal amount to substantially passivate the deactivated solution.

In this disclosure, an unbridged single site catalyst formulation wasemployed in the comparative solution process and comparative ethyleneinterpolymer products were produced. A highly active unbridged singlesite catalyst formulation was produced by optimizing the proportion ofeach of the four catalyst components: Component C, Component M^(C)(where the superscript ‘^(C)’ denotes the unbridged single site catalystformulation), Component B^(C) and Component P^(C).

In the case of one CSTR, the quantity of the bulky ligand metal complex,Component C, added to the first reactor (R1) was expressed as the partsper million (ppm) of Component C in the total mass of the solution inR1, i.e. “R1 catalyst (ppm)”. In the case of two CSTRs, the quantity ofComponent C added to R1 and R2 was controlled and expressed as the partsper million (ppm) of Component C in R1 and R2; optionally the quantityof Component C added to R3 was controlled and expressed as the parts permillion (ppm) of Component C in R3. The upper limit on the ppm ofComponent C in any reactor may be 5, in some cases 3 and is other cases2. The lower limit on the ppm of Component C in any reactor may be 0.02,in some cases 0.05 and in other cases 0.1.

The proportion of catalyst Component B^(C) was optimized by controllingthe (ionic activator)/(bulky ligand-metal complex) molar ratio,([B^(C)]/[C]), in a reactor. The upper limit on reactor ([B^(C)]/[C])may be 10, in some cases 5 and in other cases 2. The lower limit onreactor ([B^(C)]/[C]) may be 0.3, in some cases 0.5 and in other cases1.0. The proportion of catalyst Component M^(C) was optimized bycontrolling the (alumoxane)/(bulky ligand-metal complex) molar ratio,([M^(C)]/[C]), in a reactor. The alumoxane co-catalyst was generallyadded in a molar excess relative to the bulky ligand-metal complex. Theupper limit on reactor ([M^(C)]/[C]) molar ratio may be 1000, in somecases 500 and is other cases 200. The lower limit on reactor([M^(C)]/[C]) molar ratio may be 1, in some cases 10 and in other cases30. The addition of catalyst Component P^(C) is optional. If added, theproportion of Component P^(C) was optimized by controlling the (hinderedphenol)/(alumoxane) molar ratio, ([P^(C)]/[M^(C)]), in any reactor. Theupper limit on reactor ([P^(C)]/[M^(C)]) molar ratio may be 1.0, in somecases 0.75 and in other cases 0.5. The lower limit on reactor([P^(C)]/[M^(C)]) molar ratio may be 0.0, in some cases 0.1 and in othercases 0.2.

Interpolymers

The first ethylene interpolymer was synthesized by a bridged metallocenecatalyst formulation. Referring to the embodiment shown in FIG. 6 , ifthe optional α-olefin is not added to reactor 11 a (R1), then the firstethylene interpolymer is an ethylene homopolymer. If an α-olefin isadded, the following weight ratio is one parameter to control thedensity of the first ethylene interpolymer ((α-olefin)/(ethylene))^(R1).The upper limit on ((α-olefin)/(ethylene))^(R1) may be about 3; in othercases about 2 and in still other cases about 1. The lower limit on((α-olefin)/(ethylene))^(R1) may be 0; in other cases about 0.25 and instill other cases about 0.5. Hereafter, the symbol “σ¹” refers to thedensity of the first ethylene interpolymer produced in R1, i.e. reactor11 a in FIG. 6 or reactor 111 a in FIG. 7 . The upper limit on σ¹ may be0.975 g/cc; in some cases, 0.965 g/cc and, in other cases, 0.955 g/cc.The lower limit on σ¹ may be 0.855 g/cc, in some cases 0.865 g/cc, and,in other cases 0.875 g/cc. Density decreases as the content of one ormore α-olefins in the first ethylene interpolymer increases. Theα-olefin content was expressed as the mole percent of α-olefin in thefirst ethylene interpolymer. The upper limit on the mole percent ofα-olefin(s) in the first ethylene interpolymer may be 25%; in somecases, 23% and in other cases 20%. The lower limit on the mole percentof α-olefin in the first ethylene interpolymer was 0%, i.e. no α-olefinwas added to the solution polymerization process and the first ethyleneinterpolymer was an ethylene homopolymer.

Methods to determine the CDBI₅₀ (Composition Distribution BranchingIndex) of an ethylene interpolymer are well known to those skilled inthe art. The CDBI₅₀, expressed as a percent, was defined as the percentof the ethylene interpolymer whose comonomer (α-olefin) composition iswithin 50% of the median comonomer composition. It is also well known tothose skilled in the art that the CDBI₅₀ of ethylene interpolymersproduced with homogeneous catalyst formulations are higher relative tothe CDBI₅₀ of α-olefin containing ethylene interpolymers produced withheterogeneous catalyst formulations. The upper limit on the CDBI₅₀ ofthe first ethylene interpolymer may be 98%, in other cases 95% and instill other cases 90%. The lower limit on the CDBI₅₀ of the firstethylene interpolymer may be 70%, in other cases 75% and in still othercases 80%.

The upper limit on the M_(w)/M_(n) of the first ethylene interpolymermay be 2.4, in other cases 2.3 and in still other cases 2.2. The lowerlimit on the M_(w)/M_(n) the first ethylene interpolymer may be 1.7, inother cases 1.8 and in still other cases 1.9.

The first ethylene interpolymer contains long chain branching ascharacterized by the dimensionless nonlinear rheology network parameter‘Δ_(int.)’ discussed above. The upper limit on the Δ_(int.) of the firstethylene interpolymer may be 0.09, in other cases 0.07 and in stillother cases 0.05 (dimensionless). The lower limit on the Δ_(int.) of thefirst ethylene interpolymer may be greater than or equal to 0.01, inother cases greater than 0.015 and in still other cases greater than0.02 (dimensionless).

The first ethylene interpolymer has an Unsaturation Ratio, UR, definedby Eq.(UR) discussed above. The upper limit on the UR of the firstethylene interpolymer may be 0.06, in other cases 0.04 and in stillother cases 0.02 (dimensionless). The lower limit on the UR of the firstethylene interpolymer may be −0.40, in other cases −0.30 and in stillother cases −0.20 (dimensionless).

The first ethylene interpolymer contained ‘a residual catalytic metal’that reflected the chemical composition of the bridged metallocenecatalyst formulation injected into the first reactor. Residual catalyticmetal was quantified by Neutron Activation Analysis (NAA), i.e. theparts per million (ppm) of catalytic metal in the first ethyleneinterpolymer, where the catalytic metal originated from the metal inComponent A (Formula (I)); this metal will be referred to as “metalA^(R1)”. Non-limiting examples of metal A^(R1) include Group 4 metals,titanium, zirconium and hafnium. In the case of an ethylene interpolymerproduct that contains one interpolymer, i.e. the first ethyleneinterpolymer, the residual catalytic metal is equal to the ppm metalA^(R1) in the ethylene interpolymer product. The upper limit on the ppmof metal A^(R1) in the first ethylene interpolymer may be 5.0 ppm, inother cases 4.0 ppm and in still other cases 3.0 ppm. The lower limit onthe ppm of metal A^(R1) in the first ethylene interpolymer may be 0.03ppm, in other cases 0.09 ppm and in still other cases 0.15 ppm.

The amount of hydrogen added to R1 can vary over a wide range allowingthe continuous solution process to produce first ethylene interpolymersthat differ in melt index, hereafter I₂ ¹ (melt index is measured at190° C. using a 2.16 kg load following the procedures outlined in ASTMD1238). This is accomplished by adjusting the hydrogen flow rate instream 4 (FIG. 6 ). The quantity of hydrogen added to reactor 11 a (R1)is expressed as the parts-per-million (ppm) of hydrogen in R1 relativeto the total mass in reactor R1; hereinafter H₂ ^(R1) (ppm). In somecases, H₂ ^(R1) (ppm) ranges from 100 ppm to 0 ppm, in other cases from50 ppm to 0 ppm, in alternative cases from 20 to 0 and in still othercases from 2 ppm to 0 ppm. The upper limit on I₂ ¹ may be 200 dg/min, insome cases 100 dg/min; in other cases, 50 dg/min, and, in still othercases 1 dg/min. The lower limit on I₂ ¹ may be 0.01 dg/min, in somecases 0.05 dg/min; in other cases, 0.1 dg/min, and, in still other cases0.5 dg/min.

The upper limit on the weight percent (wt. %) of the first ethyleneinterpolymer in the ethylene interpolymer product may be 100 wt. %, insome cases 60 wt. %, in other cases 55 wt. % and in still other cases 50wt. %. The lower limit on the wt. % of the first ethylene interpolymerin the ethylene interpolymer product may be 5 wt. %; in other cases, 8wt. % and in still other cases 10 wt. %.

The second ethylene interpolymer, may, or may not, be present. FIG. 6illustrates an embodiment where the second ethylene interpolymer is notpresent, i.e. where one CSTR was used and stream 11 c was deactivated(via deactivator tank 18A). Turning to FIG. 7 , a second ethyleneinterpolymer was synthesized by injecting a bridged metallocene catalystformulation into the second solution polymerization reactor 112 a (orR2). If optional α-olefin is not added to reactor 112 a (R2) eitherthrough fresh α-olefin stream 108 or carried over from reactor 111 a(R1) in stream 111 e (series mode), then the second ethyleneinterpolymer was an ethylene homopolymer. If α-olefin was present in R2,the following weight ratio was one parameter to control the density ofthe second ethylene interpolymer ((α-olefin)/(ethylene))^(R2). The upperlimit on ((α-olefin)/(ethylene))^(R2) may be 3; in other cases 2 and instill other cases 1. The lower limit on ((α-olefin)/(ethylene))^(R2) maybe 0; in other cases 0.25 and in still other cases 0.5. Hereafter, thesymbol “σ²” refers to the density of the second ethylene interpolymer.The upper limit on σ² may be 0.975 g/cc; in some cases, 0.965 g/cc and,in other cases 0.955 g/cc. The lower limit on σ² may be 0.855 g/cc, insome cases 0.865 g/cc, and, in other cases 0.875 g/cc. The upper limiton the mole percent of one or more α-olefins in the second ethyleneinterpolymer may be 25%; in some cases, 23% and in other cases 20%. Thelower limit on the mole percent of α-olefin in the second ethyleneinterpolymer was 0%, i.e. no α-olefin was added to the solutionpolymerization process and the second ethylene interpolymer was anethylene homopolymer.

The upper limit on the CDBI₅₀ of the second ethylene interpolymer may be98%, in other cases 95% and in still other cases 90%. The lower limit onthe CDBI₅₀ of the second ethylene interpolymer may be 70%, in othercases 75% and in still other cases 80%.

The upper limit on the M_(w)/M_(n) of the second ethylene interpolymermay be 2.4, in other cases 2.3 and in still other cases 2.2. The lowerlimit on the M_(w)/M_(n) the second ethylene interpolymer may be 1.7, inother cases 1.8 and in still other cases 1.9.

The second ethylene interpolymer contains long chain branching ascharacterized by the dimensionless nonlinear rheology network parameter‘Δ_(int.)’ discussed above. The upper limit on the Δ_(int.) of thesecond ethylene interpolymer may be 0.09, in other cases 0.07 and instill other cases 0.05 (dimensionless). The lower limit on the Δ_(int.)of the second ethylene interpolymer may be greater than or equal to0.01, in other cases greater than 0.015 and in still other cases greaterthan 0.02 dimensionless.

The second ethylene interpolymer has an Unsaturation Ratio, UR, definedby Eq. (UR). The upper limit on the UR of the second ethyleneinterpolymer may be 0.06, in other cases 0.04 and in still other cases0.02 (dimensionless). The lower limit on the UR of the second ethyleneinterpolymer may be −0.40, in other cases −0.30 and in still other cases−0.20 (dimensionless).

The catalyst residue in the second ethylene interpolymer reflects theamount of the bridged metallocene catalyst formulation employed in R2 orthe amount of Component A employed in R2. The species of Component A(Formula (I)) containing ‘metal A^(R2)’ employed in second reactor maydiffer from the species of Component A employed in the first reactor. Inthe case of a pure sample of the second ethylene interpolymer, the upperlimit on the ppm of metal A^(R2) in the second ethylene interpolymer maybe 5.0 ppm, in other cases 4.0 ppm and in still other cases 3.0 ppm;while the lower limit on the ppm of metal A^(R2) in the second ethyleneinterpolymer may be 0.03 ppm, in other cases 0.09 ppm and in still othercases 0.15 ppm.

Referring to the embodiments shown in FIG. 7 , the amount of hydrogenadded to R2 can vary over a wide range which allows the continuoussolution polymerization process to produce second ethylene interpolymersthat differ in melt index, hereinafter I₂ ². This is accomplished byadjusting the hydrogen flow rate in stream 109. The quantity of hydrogenadded was expressed as the parts-per-million (ppm) of hydrogen in R2relative to the total mass in reactor R2; hereinafter H₂ ^(R2) (ppm). Insome cases, H₂ ^(R2) (ppm) ranges from 100 ppm to 0 ppm, in some casesfrom 50 ppm to 0 ppm, in other cases from 20 to 0 and in still othercases from 2 ppm to 0 ppm. The upper limit on I₂ ² may be 1000 dg/min;in some cases, 750 dg/min; in other cases, 500 dg/min, and, in stillother cases 200 dg/min. The lower limit on I₂ ² may be 0.3 dg/min, insome cases 0.4 dg/min, in other cases 0.5 dg/min, and; in still othercases 0.6 dg/min.

The upper limit on the weight percent (wt. %) of the second ethyleneinterpolymer in the ethylene interpolymer product may be 95 wt. %, inother cases 92 wt. % and in still other cases 90 wt. %. The lower limiton the wt. % of the second ethylene interpolymer in the ethyleneinterpolymer product may be 0 wt. %, in some cases 20 wt. %, in othercases 30 wt. % and in still other cases 40 wt. %.

Optionally, embodiments of ethylene interpolymer products contained athird ethylene interpolymer. Referring to FIG. 6 , a third ethyleneinterpolymer was produced in reactor 17 (R3) if catalyst deactivator Awas not added upstream of reactor 17. Referring to FIG. 7 , a thirdethylene interpolymer was produced in reactor 117 if catalystdeactivator was not added upstream of reactor 117. If α-olefin was notadded, the third ethylene interpolymer was an ethylene homopolymer. Ifα-olefin was present in R3, the following weight ratio was one parameterthat determined the density of the third ethylene interpolymer:((α-olefin)/(ethylene))^(R). The upper limit on((α-olefin)/(ethylene))^(R3) may be 3; in other cases 2 and in stillother cases 1. The lower limit on ((α-olefin)/(ethylene))^(R3) may be 0;in other cases 0.25 and in still other cases 0.5. Hereinafter, thesymbol “σ₃” refers to the density of the third ethylene interpolymer.The upper limit on σ³ may be 0.975 g/cc; in some cases, 0.965 g/cc and,in other cases, 0.955 g/cc. The lower limit on σ³ may be 0.855 g/cc, insome cases 0.865 g/cc, and, in other cases 0.875 g/cc. The upper limiton the mole percent of one or more α-olefins in the third ethyleneinterpolymer may be 25%; in some cases, 23% and in other cases 20%. Thelower limit on the mole percent of α-olefin in the third ethyleneinterpolymer was 0%, i.e. no α-olefin was added to the solutionpolymerization process and the third ethylene interpolymer was anethylene homopolymer.

One or more of the following homogeneous catalyst formulations may beinjected into R3: the bridged metallocene catalyst formulation, theunbridged single site catalyst formulation or a homogeneous catalystformulation that contains a bulky ligand-metal complex that is not amember of the genera defined by Formula (I) or Formula (II). FIGS. 6 and7 illustrates the injection of a homogeneous catalyst formulation intoreactor 17 or 117, respectively, through stream 40 or 140, respectively.This disclosure includes embodiments where a heterogeneous catalystformulation was injected into the third reactor (R3). FIG. 6 illustratesa non-limiting example were a heterogeneous catalyst assembly (streams34 a-34 e and 34 h) was employed to produce and inject an on-lineZiegler-Natta catalyst formulation into reactor 17. Similarly, FIG. 7illustrates a non-limiting example were a heterogeneous catalystassembly (streams 134 a-134 e and 134 h) was employed to produce andinject an on-line Ziegler-Natta catalyst formulation into reactor 117.

The upper limit on the CDBI₅₀ of the third ethylene interpolymer may be98%, in other cases 95% and in still other cases 90%. The lower limit onthe CDBI₅₀ of the optional third ethylene interpolymer may be 35%, inother cases 40% and in still other cases 45%.

The upper limit on the M_(w)/M_(n) of the third ethylene interpolymermay be 5.0, in other cases 4.8 and in still other cases 4.5. The lowerlimit on the M_(w)/M_(n) of the optional third ethylene interpolymer maybe 1.7, in other cases 1.8 and in still other cases 1.9.

If the bridged metallocene catalyst formulation was employed in thethird reactor the third ethylene interpolymer contained long chainbranching as characterized by the dimensionless nonlinear rheologynetwork parameter ‘Δ_(int.)’ discussed above. The upper limit on theΔ_(int.) of the third ethylene interpolymer may be 0.09, in other cases0.07 and in still other cases 0.05 (dimensionless). The lower limit onthe Δ_(int.) of the third ethylene interpolymer may be greater than orequal to 0.01, in other cases greater than 0.015, and in still othercases greater than 0.02 (dimensionless). If the unbridged single sitecatalyst formulation was employed in the third reactor the thirdethylene interpolymer contained an undetectable amount of long chainbranching, i.e. the third ethylene interpolymer has a dimensionlessΔ_(int.) value less than 0.01. If a heterogeneous catalyst formulationwas employed in the third reactor the third ethylene interpolymercontained an undetectable amount of long chain branching. If ahomogeneous catalyst formulation containing a bulky ligand-metal complexthat is not a member of the genera defined by Formula (I) or Formula(II) was employed in R3, the third ethylene interpolymer may, or maynot, contain LCB.

If the third ethylene interpolymer was synthesized by the bridgedmetallocene catalyst formulation, the third ethylene interpolymer wascharacterized by an Unsaturation Ratio, UR; where the upper limit on URwas 0.06, in other cases 0.04 and in still other cases 0.02(dimensionless) and the lower limit on UR was −0.40, in other cases−0.30 and in still other cases −0.20 (dimensionless). If the thirdethylene interpolymer was synthesized by the unbridged single sitecatalyst formulation, the third ethylene interpolymer was characterizedby an Unsaturation Ratio, UR; where the upper limit on UR was −0.1, inother cases −0.2 and in still other cases −0.3 and the lower limit on URwas −0.8, in other cases −0.65 and in still other cases −0.5. If thethird ethylene interpolymer was synthesized by a Ziegler-Natta catalystformulation, the third ethylene interpolymer was characterized by the anUnsaturation Ratio, UR; where the upper limit on UR was −0.7, in othercases −0.75 and in still other cases −0.8 and the lower limit on UR was−1.0, in other cases −0.95 and in still other cases −0.9.

The catalyst residue in the third ethylene interpolymer reflected thecatalyst employed in its manufacture. If the bridged metallocenecatalyst formulation was used, the species of Component A (Formula (I))containing ‘metal A^(R3)’ employed in the third reactor may differ fromthe species employed in R1, or R1 and R2. In other words, the catalyticmetal employed in R3 may differ from the catalytic metal employed in R1and/or R2. In the case of a pure sample of the third ethyleneinterpolymer, the upper limit on the ppm of metal A^(R3) in the thirdethylene interpolymer may be 5.0 ppm, in other cases 4.0 ppm and instill other cases 3.0 ppm; while the lower limit on the ppm of metalA^(R3) in the third ethylene interpolymer may be 0.03 ppm, in othercases 0.09 ppm and in still other cases 0.15 ppm.

The third ethylene interpolymer may be synthesized using an unbridgedsingle site catalyst formulation comprising Component C and a catalytic‘metal C^(R3)”. Non-limiting examples of metal C^(R3) include the Group4 metals titanium, zirconium and hafnium. In the case of a pure sampleof the third ethylene interpolymer, the upper limit on the ppm of metalC^(R3) in the third ethylene interpolymer may be 3.0 ppm, in other cases2.0 ppm and in still other cases 1.5 ppm. The lower limit on the ppm ofmetal C^(R3) in the third ethylene interpolymer may be 0.03 ppm, inother cases 0.09 ppm and in still other cases 0.15 ppm.

The third ethylene interpolymer may be synthesized using a homogeneouscatalyst formulation that contains a bulky ligand-metal complex,containing metal ‘B^(R3)’, that is not a member of the genera defined byFormula (I) or Formula (II). Non-limiting examples of metal B^(R3)include the Group 4 metals titanium, zirconium and hafnium. In the caseof a pure sample of the third ethylene interpolymer, the upper limit onthe ppm of metal B^(R3) in the third ethylene interpolymer may be 5.0ppm, in other cases 4.0 ppm and in still other cases 3.0 ppm. The lowerlimit on the ppm of metal B^(R3) in the third ethylene interpolymer maybe 0.03 ppm, in other cases 0.09 ppm and in still other cases 0.15 ppm.

The third ethylene interpolymer may be synthesized using a heterogeneouscatalyst formulation. A non-limiting example of a heterogeneous catalystformulation is an in-line Ziegler-Natta catalyst formulation; FIGS. 6and 7 illustrate the injection of in-line Ziegler-Natta catalystformulations into tubular reactor 17 or 117, respectively, throughstreams 34 e or 134 e, respectively. The in-line Ziegler-Natta catalystformulation comprises a metal compound (component (vii)) and the term‘metal Z^(R3)’ refers to the metal in this compound. Non-limitingexamples of metal Z^(R3) include metals selected from Group 4 throughGroup 8 of the Periodic Table. In the case of a pure sample of the thirdethylene interpolymer, the upper limit on the ppm of metal Z^(R3) in thethird ethylene interpolymer may be 12 ppm, in other cases 10 ppm and instill other cases 8 ppm; while the lower limit on the ppm of metalZ^(R3) in the third ethylene interpolymer may be 0.5 ppm, in other cases1 ppm and in still other cases 3 ppm.

Referring to the embodiments shown in FIGS. 6 and 7 , optional hydrogenmay be injected into the tubular reactor 17 or 117, respectively,through stream 16 or stream 116, respectively. The amount of hydrogenadded to R3 may vary over a wide range. Adjusting the amount of hydrogenin R3, hereinafter H₂ ^(R3) (ppm), allows the continuous solutionprocess to produce third ethylene interpolymers that differ widely inmelt index, hereinafter I₂ ³. The amount of optional hydrogen added toR3 ranges from 100 ppm to 0 ppm, in some cases from 50 ppm to 0 ppm, inother cases from 20 to 0 and in still other cases from 2 ppm to 0 ppm.The upper limit on I₂ ³ may be 2000 dg/min; in some cases, 1500 dg/min;in other cases, 1000 dg/min, and; in still other cases 500 dg/min. Thelower limit on I₂ ³ may be 0.4 dg/min, in some cases 0.6 dg/min, inother cases 0.8 dg/min, and; in still other cases 1.0 dg/min.

The upper limit on the weight percent (wt. %) of the optional thirdethylene interpolymer in the ethylene interpolymer product may be 30 wt.%, in other cases 25 wt. % and in still other cases 20 wt. %. The lowerlimit on the wt. % of the optional third ethylene interpolymer in theethylene interpolymer product may be 0 wt. %; in other cases, 5 wt. %and in still other cases 10 wt. %.

Embodiments of the ethylene interpolymer product may comprise: (i) thefirst ethylene interpolymer; (ii) the first ethylene interpolymer andthe third ethylene interpolymer; (iii) the first ethylene interpolymerand the second ethylene interpolymer, or; (iv) the first ethyleneinterpolymer, the second ethylene interpolymer and the third ethyleneinterpolymer.

The upper limit on the density of the ethylene interpolymer product(ρ^(f)) may be 0.975 g/cc, in some cases, 0.965 g/cc, and, in othercases 0.955 g/cc. The lower limit on the density of the ethyleneinterpolymer product may be 0.855 g/cc, in some cases 0.865 g/cc, and,in other cases 0.875 g/cc. The upper limit on the mole percent of one ormore α-olefins in the ethylene interpolymer product may be 25%; in somecases, 23% and in other cases 20%. The lower limit on the mole percentof α-olefin in the ethylene interpolymer product was 0%, i.e. noα-olefin was added to the solution polymerization process and theethylene interpolymer product was an ethylene homopolymer.

The upper limit on the CDBI₅₀ of the ethylene interpolymer product maybe 98%, in other cases 90% and in still other cases 85%. An ethyleneinterpolymer product with a CDBI₅₀ of 97% may result if an α-olefin isnot added to the continuous solution polymerization process; in thiscase, the ethylene interpolymer product is an ethylene homopolymer. Thelower limit on the CDBI₅₀ of an ethylene interpolymer product may be 1%,in other cases 2% and in still other cases 3%.

The upper limit on the M_(w)/M_(n) of the ethylene interpolymer productdepends on the number of reactors employed and polymerizationsconditions. For example, referring to FIG. 6 , if stream 11 c isdeactivated upstream of tubular reactor 17 the upper limit on theM_(w)/M_(n) of the ethylene interpolymer product may be 2.4, in othercases 2.3 and in still other cases 2.2; while the lower limit on theM_(w)/M_(n) of this ethylene interpolymer product may be 1.7, in othercases 1.8 and in still other cases 1.9. Referring to multi-reactor FIG.7 , the upper limit on the M_(w)/M_(n) of an ethylene interpolymerproduct (comprising a first, second and optionally a third ethyleneinterpolymer) may be 25, in other cases 20 and in still other cases 15;while the lower limit on the M_(w)/M_(n) of this ethylene interpolymerproduct may be 1.8, in other cases 1.9 and in still other cases 2.0.

The ethylene interpolymer product contains long chain branching (LCB)and LCB was characterized by the dimensionless nonlinear rheologynetwork parameter ‘Δ_(int.)’ discussed above. The upper limit on theΔ_(int.) of the ethylene interpolymer product may be 0.09, in othercases 0.07 and in still other cases 0.05 (dimensionless). The lowerlimit on the Δ_(int.) of the ethylene interpolymer product may begreater than or equal to 0.01, in other cases greater than 0.015, and instill other cases greater than 0.02 (dimensionless).

If the ethylene interpolymer product was synthesized using one or morebridged metallocene catalyst formulations, the ethylene interpolymerproduct was characterized by an Unsaturation Ratio, UR; where the upperlimit on UR was 0.06, in other cases 0.04 and in still other cases 0.02(dimensionless) and the lower limit on UR was −0.40, in other cases−0.30 and in still other cases −0.20 (dimensionless). If the ethyleneinterpolymer product contained a portion of a third ethyleneinterpolymer synthesized using an unbridged single site catalystformulation, the ethylene interpolymer product was characterized by anUnsaturation Ratio, UR; where the upper limit on UR was 0.06, in othercases 0.04 and in still other cases 0.02 and the lower limit on UR was−0.8, in other cases −0.65 and in still other cases −0.5. If theethylene interpolymer product contained a portion of a third ethyleneinterpolymer synthesized using a Ziegler-Natta catalyst formulation, theethylene interpolymer product was characterized by the an UnsaturationRatio, UR; where the upper limit on UR was 0.06, in other cases 0.04 andin still other cases 0.02 and the lower limit on UR was −1.0, in othercases −0.95 and in still other cases −0.9.

Table 3 discloses the ‘residual catalytic metal’ in ethyleneinterpolymer product Examples 1-6 as determined by Neutron ActivationAnalysis (NAA). In Examples 1, 2 and 4-6 the same bridged metallocenecatalyst formulation was injected into reactors 111 a and 112 a (FIG. 7) and the residual catalytic metals in these samples varied from 1.38 to1.98 ppm Hf. In Example 3 one CSTR was employed and the bridgedmetallocene catalyst formulation was injected into reactor 11 a (FIG. 6), Example 3 had a residual catalytic metal of 2.20 ppm Hf. In Examples1-6 the quantity of titanium was below the N.A.A. detection limit. InExample 8, a bridged metallocene catalyst formulation (Hf containing)was injected into reactor 111 a and an unbridged single site catalystformulation (Ti containing) was injected into reactor 112 a.Comparatives Q1-Q4 were manufactured using a Hf-based catalystformulation and contained from 0.24-0.34 ppm Hf and undetectable Ti.Comparative 2 and Comparative 3 were manufactured using a Hf-based and aTi-based catalyst formulation. The remaining comparatives in Table 3were produced with various Ti-based catalyst formulations, i.e.Comparatives R, S, U, V, 1, 4 and 5 where the Ti content ranged from0.14 to 7.14 ppm Ti.

In embodiments where the same species of Component A was employed in oneor more reactors, the upper limit on the residual catalytic metal in theethylene interpolymer product may be 5.0 ppm, in other cases 4.0 ppm andin still other cases 3.0 ppm, and; the lower limit on the residualcatalytic metal in the ethylene interpolymer product may be 0.03 ppm, inother cases 0.09 ppm and in still other cases 0.15 ppm.

In embodiments where two or more reactors were operating and differentspecies of Component A (having different metals) were employed in eachreactor, the upper limit on the ppm of metal A^(R1) in the ethyleneinterpolymer product may be 3.0 ppm, in other cases 2.5 ppm and in stillother cases 2.0 ppm; while the lower limit on the ppm of metal A^(R1) inthe ethylene interpolymer product may be 0.0015 ppm, in other cases0.005 ppm and in still other cases 0.01 ppm.

In embodiments where the ethylene interpolymer product contained twointerpolymers and different species of Component A (having differentmetals) were employed in R1 (vessel 111 a FIG. 7 ) and R2 (vessel 112 aFIG. 7 ), the upper limit on the ppm of metal A^(R2) in the ethyleneinterpolymer product may be 5.0 ppm, in other cases 4.0 ppm and in stillother cases 3.0 ppm; while the lower limit on the ppm of metal A^(R2) inthe ethylene interpolymer product may be 0.0012 ppm, in other cases 0.04ppm and in still other cases 0.06 ppm.

In embodiments where the ethylene interpolymer product contains a thirdethylene interpolymer and different species of Component A (havingdifferent metals) were employed in R1, R2 and R3 (vessel 117 FIG. 7 )the upper limit on the ppm of metal A^(R2) in the ethylene interpolymerproduct may be 3.5 ppm, in other cases 2.5 ppm and in still other cases2.0 ppm, and; the lower limit on the ppm of metal A^(R2) in the ethyleneinterpolymer product may be 0.003 ppm, in other cases 0.01 ppm and instill other cases 0.015 ppm.

In embodiments where the ethylene interpolymer product contained a thirdethylene interpolymer and different species of Component A (havingdifferent metals) were employed in R1, R2 and R3 the upper limit on theppm of metal A^(R3) in the ethylene interpolymer product may be 1.5 ppm,in other cases 1.25 ppm and in still other cases 1.0 ppm. In embodimentswhere an unbridged single site catalyst formulation, comprising metalC^(R3), was injected into the tubular reactor the upper limit on the ppmof metal C^(R3) in the ethylene interpolymer product may be 1.0 ppm, inother cases 0.8 ppm and in still other cases 0.5 ppm. In embodimentswere a homogeneous catalyst formulation, comprising metal B^(R3), wasinjected into the tubular reactor the upper limit on the ppm of metalB^(R3) in the ethylene interpolymer product may be 1.5 ppm, in othercases 1.25 ppm and in still other cases 1.0 ppm. In embodiments were aheterogeneous catalyst formulation, comprising metal Z^(R3), wasinjected into the tubular reactor the upper limit on the ppm of metalZ^(R3) in the ethylene interpolymer product may be 3.5 ppm, in othercases 3 ppm and in still other cases 2.5 ppm. The lower limit on the ppmof metal A^(R3), C^(R3), B^(R3) or Z^(R3) in the ethylene interpolymerproduct was 0.0, i.e. a catalyst deactivator was added upstream of thetubular reactor (R3).

The upper limit on melt index of the ethylene interpolymer product maybe 500 dg/min, in some cases 400 dg/min; in other cases 300 dg/min, and;in still other cases 200 dg/min. The lower limit on the melt index ofthe ethylene interpolymer product may be 0.3 dg/min, in some cases 0.4dg/min; in other cases 0.5 dg/min, and; in still other cases 0.6 dg/min.

Manufactured Articles

The ethylene interpolymer products disclosed herein may be convertedinto flexible manufactured articles such as monolayer or multilayerfilms. Non-limiting examples of processes to prepare such films includeblown film processes, double bubble processes, triple bubble processes,cast film processes, tenter frame processes and machine directionorientation (MDO) processes.

In the blown film extrusion process an extruder heats, melts, mixes andconveys a thermoplastic, or a thermoplastic blend. Once molten, thethermoplastic is forced through an annular die to produce athermoplastic tube. In the case of co-extrusion, multiple extruders areemployed to produce a multilayer thermoplastic tube. The temperature ofthe extrusion process is primarily determined by the thermoplastic orthermoplastic blend being processed, for example the melting temperatureor glass transition temperature of the thermoplastic and the desiredviscosity of the melt. In the case of polyolefins, typical extrusiontemperatures are from 330° F. to 550° F. (166° C. to 288° C.). Upon exitfrom the annular die, the thermoplastic tube is inflated with air,cooled, solidified and pulled through a pair of nip rollers. Due to airinflation, the tube increases in diameter forming a bubble of desiredsize. Due to the pulling action of the nip rollers the bubble isstretched in the machine direction. Thus, the bubble is stretched in twodirections: the transverse direction (TD) where the inflating airincreases the diameter of the bubble; and the machine direction (MD)where the nip rollers stretch the bubble. As a result, the physicalproperties of blown films are typically anisotropic, i.e. the physicalproperties differ in the MD and TD directions; for example, film tearstrength and tensile properties typically differ in the MD and TD. Insome prior art documents, the terms “cross direction” or “CD” is used;these terms are equivalent to the terms “transverse direction” or “TD”used in this disclosure. In the blown film process, air is also blown onthe external bubble circumference to cool the thermoplastic as it exitsthe annular die. The final width of the film is determined bycontrolling the inflating air or the internal bubble pressure; in otherwords, increasing or decreasing bubble diameter. Film thickness iscontrolled primarily by increasing or decreasing the speed of the niprollers to control the draw-down rate. After exiting the nip rollers,the bubble or tube is collapsed and may be slit in the machine directionthus creating sheeting. Each sheet may be wound into a roll of film.Each roll may be further slit to create film of the desired width. Eachroll of film is further processed into a variety of consumer products asdescribed below.

The cast film process is similar in that a single or multipleextruder(s) may be used; however the various thermoplastic materials aremetered into a flat die and extruded into a monolayer or multilayersheet, rather than a tube. In the cast film process the extruded sheetis solidified on a chill roll.

In the double bubble process, a first blown film bubble is formed andcooled, then the first bubble is heated and re-inflated forming a secondblown film bubble, which is subsequently cooled. The ethyleneinterpolymer products, disclosed herein, are also suitable for thetriple bubble blown process. Additional film converting processes,suitable for the disclosed ethylene interpolymer products, includeprocesses that involve a Machine Direction Orientation (MDO) step; forexample, blowing a film or casting a film, quenching the film and thensubjecting the film tube or film sheet to a MDO process at any stretchratio. Additionally, the ethylene interpolymer product films disclosedherein are suitable for use in tenter frame processes as well as otherprocesses that introduce biaxial orientation.

Depending on the end-use application, the disclosed ethyleneinterpolymer products may be converted into films that span a wide rangeof thicknesses. Non-limiting examples include, food packaging filmswhere thicknesses may range from 0.5 mil (13 μm) to 4 mil (102 μm), and;in heavy duty sack applications film thickness may range from 2 mil (51μm) to 10 mil (254 μm).

The monolayer, in monolayer films, may contain more than one ethyleneinterpolymer product and/or one or more additional polymer; non-limitingexamples of additional polymers include ethylene polymers and propylenepolymers. The lower limit on the weight percent of the ethyleneinterpolymer product in a monolayer film may be 3 wt. %, in other cases10 wt. % and in still other cases 30 wt. %. The upper limit on theweight percent of the ethylene interpolymer product in the monolayerfilm may be 100 wt. %, in other cases 90 wt. % and in still other cases70 wt. %.

The ethylene interpolymer products disclosed herein may also be used inone or more layers of a multilayer film; non-limiting examples ofmultilayer films include three, five, seven, nine, eleven or morelayers. The disclosed ethylene interpolymer products are also suitablefor use in processes that employ micro-layering dies and/or feed-blocks,such processes can produce films having many layers, non-limitingexamples include from 10 to 10,000 layers.

The thickness of a specific layer (containing the ethylene interpolymerproduct) within a multilayer film may be 5%, in other cases 15% and instill other cases 30% of the total multilayer film thickness. In otherembodiments, the thickness of a specific layer (containing the ethyleneinterpolymer product) within a multilayer film may be 95%, in othercases 80% and in still other cases 65% of the total multilayer filmthickness. Each individual layer of a multilayer film may contain morethan one ethylene interpolymer product and/or additional thermoplastics.

Additional embodiments include laminations and coatings, wherein mono ormultilayer films containing the disclosed ethylene interpolymer productsare extrusion laminated or adhesively laminated or extrusion coated. Inextrusion lamination or adhesive lamination, two or more substrates arebonded together with a thermoplastic or an adhesive, respectively. Inextrusion coating, a thermoplastic is applied to the surface of asubstrate. These processes are well known to those experienced in theart. Frequently, adhesive lamination or extrusion lamination are used tobond dissimilar materials, non-limiting examples include the bonding ofa paper web to a thermoplastic web, or the bonding of an aluminum foilcontaining web to a thermoplastic web, or the bonding of twothermoplastic webs that are chemically incompatible, e.g. the bonding ofan ethylene interpolymer product containing web to a polyester orpolyamide web. Prior to lamination, the web containing the disclosedethylene interpolymer product(s) may be monolayer or multilayer. Priorto lamination the individual webs may be surface treated to improve thebonding, a non-limiting example of a surface treatment is coronatreating. A primary web or film may be laminated on its upper surface,its lower surface, or both its upper and lower surfaces with a secondaryweb. A secondary web and a tertiary web could be laminated to theprimary web; wherein the secondary and tertiary webs differ in chemicalcomposition. As non-limiting examples, secondary or tertiary webs mayinclude; polyamide, polyester and polypropylene, or webs containingbarrier resin layers such as EVOH. Such webs may also contain a vapordeposited barrier layer; for example, a thin silicon oxide (SiO_(x)) oraluminum oxide (AlO_(x)) layer. Multilayer webs (or films) may containthree, five, seven, nine, eleven or more layers.

The ethylene interpolymer products disclosed herein can be used in awide range of manufactured articles comprising one or more films(monolayer or multilayer). Non-limiting examples of such manufacturedarticles include: food packaging films (fresh and frozen foods, liquidsand granular foods), stand-up pouches, retortable packaging andbag-in-box packaging; barrier films (oxygen, moisture, aroma, oil, etc.)and modified atmosphere packaging; light and heavy duty shrink films andwraps, collation shrink film, pallet shrink film, shrink bags, shrinkbundling and shrink shrouds; light and heavy duty stretch films, handstretch wrap, machine stretch wrap and stretch hood films; high clarityfilms; heavy-duty sacks; household wrap, overwrap films and sandwichbags; industrial and institutional films, trash bags, can liners,magazine overwrap, newspaper bags, mail bags, sacks and envelopes,bubble wrap, carpet film, furniture bags, garment bags, coin bags, autopanel films; medical applications such as gowns, draping and surgicalgarb; construction films and sheeting, asphalt films, insulation bags,masking film, landscaping film and bags; geomembrane liners formunicipal waste disposal and mining applications; batch inclusion bags;agricultural films, mulch film and green house films; in-storepackaging, self-service bags, boutique bags, grocery bags, carry-outsacks and t-shirt bags; oriented films, machine direction oriented (MDO)films, biaxially oriented films and functional film layers in orientedpolypropylene (OPP) films, e.g. sealant and/or toughness layers.Additional manufactured articles comprising one or more films containingat least one ethylene interpolymer product include laminates and/ormultilayer films; sealants and tie layers in multilayer films andcomposites; laminations with paper; aluminum foil laminates or laminatescontaining vacuum deposited aluminum; polyamide laminates; polyesterlaminates; extrusion coated laminates, and; hot-melt adhesiveformulations. The manufactured articles summarized in this paragraphcontain at least one film (monolayer or multilayer) comprising at leastone embodiment of the disclosed ethylene interpolymer products.

Desired film physical properties (monolayer or multilayer) typicallydepend on the application of interest. Non-limiting examples ofdesirable film properties include: optical properties (gloss, haze andclarity), dart impact, Elmendorf tear, modulus (1% and 2% secantmodulus), tensile properties (yield strength, break strength, elongationat break, toughness, etc.), heat sealing properties (heat sealinitiation temperature, SIT, and hot tack). Specific hot tack andheat-sealing properties are desired in high speed vertical andhorizontal form-fill-seal processes that load and seal a commercialproduct (liquid, solid, paste, part, etc.) inside a pouch-like package.

In addition to desired film physical properties, it is desired that thedisclosed ethylene interpolymer products are easy to process on filmlines. Those skilled in the art frequently use the term “processability”to differentiate polymers with improved processability, relative topolymers with inferior processability. A commonly used measure toquantify processability is extrusion pressure; more specifically, apolymer with improved processability has a lower extrusion pressure (ona blown film or a cast film extrusion line) relative to a polymer withinferior processability.

The ethylene interpolymer products disclosed herein have improved bubblestability, e.g. relative to the Comparative 1 products disclosed herein.Improved bubble stability allows one to produce mono or multilayer filmsat higher production rates. Melt strength, measured in centi-Newtons(cN), is frequently used as a measure of bubble stability; i.e. thehigher the melt strength the higher the bubble stability. As shown inTable 5A and 5B, Example 1 (4.56 cN) and Example 2 (3.2 cN) have highermelt strengths relative to Comparative 15 (2.78 cN) and Comparative 16(3.03). In other words, the ethylene interpolymer products disclosedherein have an improved melt strength of from 65% to 25%, relative tocomparatives.

The films used in the manufactured articles described in this sectionmay optionally include, depending on its intended use, additives andadjuvants. Non-limiting examples of additives and adjuvants include,anti-blocking agents, antioxidants, heat stabilizers, slip agents,processing aids, anti-static additives, colorants, dyes, fillermaterials, light stabilizers, light absorbers, lubricants, pigments,plasticizers, nucleating agents and combinations thereof.

The processes disclosed herein are also capable of making ethyleneinterpolymer products that have a useful combination of desirablephysical properties for use in rigid applications or rigid articles.Non-limiting examples of rigid articles include: deli containers,margarine tubs, drink cups and produce trays; household and industrialcontainers, cups, bottles, pails, crates, tanks, drums, bumpers, lids,industrial bulk containers, industrial vessels, material handlingcontainers, bottle cap liners, bottle caps, living hinge closures; toys,playground equipment, recreational equipment, boats, marine and safetyequipment; wire and cable applications such as power cables,communication cables and conduits; flexible tubing and hoses; pipeapplications including both pressure pipe and non-pressure pipe markets,e.g. natural gas distribution, water mains, interior plumbing, stormsewer, sanitary sewer, corrugated pipes and conduit; foamed articlesmanufactured from foamed sheet or bun foam; military packaging(equipment and ready meals); personal care packaging, diapers andsanitary products; cosmetic, pharmaceutical and medical packaging, and;truck bed liners, pallets and automotive dunnage. The rigid manufacturedarticles summarized in this paragraph contain one or more of theethylene interpolymer products disclosed herein or a blend of at leastone of the ethylene interpolymer products disclosed herein with at leastone other thermoplastic.

Such rigid manufactured articles may be fabricated using the followingnon-limiting processes: injection molding, compression molding, blowmolding, rotomolding, profile extrusion, pipe extrusion, sheetthermoforming and foaming processes employing chemical or physicalblowing agents.

The desired physical properties of rigid manufactured articles depend onthe application of interest. Non-limiting examples of desired propertiesinclude: flexural modulus (1% and 2% secant modulus); tensile toughness;environmental stress crack resistance (ESCR); slow crack growthresistance (PENT); abrasion resistance; shore hardness; deflectiontemperature under load; VICAT softening point; IZOD impact strength; ARMimpact resistance; Charpy impact resistance, and; color (whitenessand/or yellowness index).

The rigid manufactured articles described in this section may optionallyinclude, depending on its intended use, additives and adjuvants.Non-limiting examples of additives and adjuvants include, antioxidants,slip agents, processing aids, anti-static additives, colorants, dyes,filler materials, heat stabilizers, light stabilizers, light absorbers,lubricants, pigments, plasticizers, nucleating agents and combinationsthereof.

Additional Embodiments

The following paragraphs disclose additional embodiments of thedisclosed ethylene interpolymer products.

An ethylene interpolymer product comprising: (i) a first ethyleneinterpolymer; (ii) a second ethylene interpolymer, and; (iii) optionallya third ethylene interpolymer; wherein said ethylene interpolymerproduct has: a) a dimensionless nonlinear rheology network parameter,Δ_(int.), greater than or equal to 0.01, satisfying the inequality[0.01×(Z−50)_(0.78)≤Δ_(int.)≤0.01×(Z−60)^(0.78)] wherein Z is anormalized molecular weight defined by

$Z = \frac{M_{w}}{M_{e}}$where M_(w) and M_(e) are the weight average molecular weight andmolecular weight between entanglements of said ethylene interpolymer,respectively, and; b) a residual catalytic metal of from ≥0.03 to ≤5 ppmof hafnium, in said ethylene interpolymer product. Other embodiments ofthe ethylene interpolymer products described in this paragraph may havea melt index from about 0.3 to about 500 dg/minute, a density from about0.855 to about 0.975 g/cc, a M_(w)/M_(n) from about 1.7 to about 25 anda CDBI₅₀ from about 1% to about 98%. Other embodiments of the ethyleneinterpolymer products described in this paragraph may contain: from 5 to60 weight percent of the first ethylene interpolymer having a melt indexfrom 0.01 to 200 dg/min and a density of 0.855 g/cc to 0.975 g/cc; from20 to 95 weight percent of the second ethylene interpolymer having amelt index from 0.3 to 1000 dg/min and a density of 0.855 g/cc to 0.975g/cc, and; optionally from 0 to 30 weight percent of the third ethyleneinterpolymer having a melt index from 0.5 to 2000 dg/min and a densityof 0.855 g/cc to 0.975 g/cc; where weight percent is the weight of saidfirst, said second or said optional third ethylene interpolymer,individually, divided by the weight of said ethylene interpolymerproduct. Other embodiments of the ethylene interpolymer productsdescribed in this paragraph may contain from 0 to about 25 mole percentof one or more α-olefin; non-limiting examples of α-olefins include C₃to C₁₀ α-olefins. Other embodiments of the ethylene interpolymerproducts may be manufactured in a solution polymerization process. Thefirst and second ethylene interpolymers, in the ethylene interpolymerproducts of this paragraph, may be synthesized using a bridgedmetallocene catalyst formulation that comprises a Component A defined byFormula (I)

wherein M is a metal selected from titanium, hafnium and zirconium; G isthe element carbon, silicon, germanium, tin or lead; X represents ahalogen atom, R₆ groups are independently selected from a hydrogen atom,a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryloxide radical, these radicals may be linear, branched or cyclic orfurther substituted with halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀alkoxy radicals, C₆₋₁₀ aryl or aryloxy radicals; R₁ represents ahydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or aC₆₋₁₀ aryl oxide radical; R₂ and R₃ are independently selected from ahydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or aC₆₋₁₀ aryl oxide radical, and; R₄ and R₅ are independently selected froma hydrogen atom, a C₁₋₂₀ hydrocarbyl radial, a C₁₋₂₀ alkoxy radical or aC₆₋₁₀ aryl oxide radical. The bridged metallocene catalyst formulationmay further comprise: a component M, comprising an alumoxaneco-catalyst; a component B, comprising a boron ionic activator, and;optionally, a component P, comprising a hindered phenol. The optionalthird ethylene interpolymer may be synthesized using a homogeneouscatalyst formulation or a heterogeneous catalyst formulation;non-limiting examples of homogeneous catalyst formulations includebridged metallocene catalyst formulations or unbridged single sitecatalyst formulations; non-limiting examples of heterogeneous catalystformulations include in-line Ziegler-Natta catalyst formulations orbatch Ziegler-Natta catalyst formulations. Optionally a heterogeneouscatalyst formulation comprising metal Z^(R3) may be injected into thetubular reactor, in this case embodiments of ethylene interpolymerproducts may contain from 0.1 to 3.5 ppm of metal Z^(R3).

Other embodiments include: a continuous solution polymerization processcomprising: i) injecting ethylene, a process solvent, a bridgedmetallocene catalyst formulation, optionally one or more α-olefins andoptionally hydrogen into a first reactor to produce a first exit streamcontaining a first ethylene interpolymer in said process solvent; ii)passing said first exit stream into a second reactor and injecting intosaid second reactor, ethylene, said process solvent, said bridgedmetallocene catalyst formulation, optionally one or more α-olefins andoptionally hydrogen to produce a second exit stream containing a secondethylene interpolymer and said first ethylene interpolymer in saidprocess solvent; iii) passing said second exit stream into a thirdreactor and optionally injecting into said third reactor, ethylene,process solvent, one or more α-olefins, hydrogen and a homogeneouscatalyst formulation or a heterogeneous catalyst formulation to producea third exit stream containing an third ethylene interpolymer, saidsecond ethylene interpolymer and said first ethylene interpolymer insaid process solvent; iv) phase separating said third exit stream torecover an ethylene interpolymer product comprising said first ethyleneinterpolymer, said second ethylene interpolymer and said optional thirdethylene interpolymer; where said continuous solution polymerizationprocess is improved by having (a) and/or (b):

(a) at least a 70% reduced [α-olefin/ethylene] weight ratio as definedby the following formula

${\%{{Reduced}\left\lbrack \frac{\alpha - {olefin}}{{ethy}lene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha - {olefin}}{{ethy}lene} \right)^{A} - \left( \frac{\alpha - {olefin}}{{ethy}lene} \right)^{C}}{\left( \frac{\alpha - {olefin}}{{ethy}lene} \right)^{C}} \right\}} \leq {{- 7}0\%}}$

wherein (α-olefin/ethylene)^(A) is calculated by dividing the weight ofsaid α-olefin added to said first reactor by the weight of said ethyleneadded to said first reactor, wherein said first ethylene interpolymerhaving a target density is produced by said bridged metallocene catalystformulation, and; (α-olefin/ethylene)^(C) is calculated by dividing theweight of said α-olefin added to said first reactor by the weight ofsaid ethylene added to said first reactor, wherein a control ethyleneinterpolymer having said target density is produced by replacing saidbridged metallocene catalyst formulation with an unbridged single sitecatalyst formulation;

(b) at least a 5% improved weight average molecular weight as defined bythe following formula

%ImprovedM_(w) = 100% × (M_(w)^(A) − M_(w)^(C))/M_(w)^(C) ≥ 10%

wherein M_(w) ^(A) is a weight average molecular weight of said firstethylene interpolymer and M_(w) ^(C) is a weight average molecularweight of a comparative ethylene interpolymer; wherein said comparativeethylene interpolymer is produced in said first reactor by replacingsaid bridged metallocene catalyst formulation with said unbridged singlesite catalyst formulation. Additional steps of this process maycomprise: a) optionally adding a catalyst deactivator A to said secondexit stream, downstream of said second reactor, forming a deactivatedsolution A; b) adding a catalyst deactivator B to said third exitstream, downstream of said third reactor, forming a deactivated solutionB; with the proviso that step b) is skipped if said catalyst deactivatorA is added in step a); c) phase separating said deactivated solution Aor B to recover said ethylene interpolymer product. If a heterogeneouscatalyst formulation was added to the third reactor, additional processsteps may comprise: d) adding a passivator to said deactivated solutionA or B forming a passivated solution, with the proviso that step d) isskipped if said heterogeneous catalyst formulation is not added to saidthird reactor, and; e) phase separating said deactivated solution A orB, or said passivated solution, to recover said ethylene interpolymerproduct. The bridged metallocene catalyst formulation may comprise: abulky ligand-metal complex ‘Component A’; a component M, comprising analumoxane co-catalyst; a component B, comprising a boron ionicactivator, and; optionally, a component P, comprising a hindered phenol;wherein the following mole ratios may be employed: a molar ratio of saidcomponent B to said component A from about 0.3:1 to about 10:1; a molarratio of said component M to said component A from about 1:1 to about300:1, and; a molar ratio of said optional component P to said componentM^(A) from 0.0:1 to about 1:1. Non-limiting examples of components M, Band P include: methylalumoxane (MMAO-7); trityl tetrakis(pentafluoro-phenyl) borate; and 2,6-di-tert-butyl-4-ethylphenol,respectively. The process may further comprise the injection of saidbridged metallocene catalyst formulation into said first reactor andoptionally said second reactor at a catalyst inlet temperature fromabout 20° C. to about 70° C.; optionally, said component M and saidcomponent P may be deleted from said bridged metallocene catalystformulation and replaced with a component J defined by the formulaAl(R¹)_(n)(OR²)_(o), wherein the (R¹) groups may be the same ordifferent hydrocarbyl groups having from 1 to 10 carbon atoms; the (OR²)groups may be the same or different, alkoxy or aryloxy groups, whereinR² is a hydrocarbyl group having from 1 to 10 carbon atoms bonded tooxygen, and; (n+o)=3, with the proviso that n is greater than 0.Optionally, said bridged metallocene catalyst formulation may beinjected into said reactors at a catalyst inlet temperature from 80° C.to 180° C. Optionally said homogeneous catalyst formulation injectedinto said third reactor is said bridged metallocene formulation, saidsingle site catalyst formulation, or a homogeneous catalyst formulationwherein the bulky metal-ligand complex is not a member of the generadefined by Formula (I) or (II). Optionally, said heterogeneous catalystformulation injected into said third reactor is an in-line Ziegler-Nattacatalyst formulation or a batch Ziegler-Natta catalyst formulation. Thein-line Ziegler-Natta catalyst formulation is formed in an in-lineprocess comprising: i) forming a first product mixture in an in-lineheterogeneous catalyst assembly by combining a stream S1 and a stream S2and allowing said first product mixture to equilibrate for a HUT-1seconds; wherein said stream S1 comprises a magnesium compound and analuminum alkyl in said process solvent and said stream S2 comprises achloride compound in said process solvent; ii) forming a second productmixture in said in-line heterogeneous catalyst assembly by combiningsaid first product mixture with a stream S3 and allowing said secondproduct mixture to equilibrate for a HUT-2 seconds; wherein said streamS3 comprises a metal compound in said process solvent; iii) forming saidin-line Ziegler-Natta catalyst formulation in said in-line heterogeneouscatalyst assembly by combining said second product mixture with a streamS4 and allowing said in-line Ziegler-Natta catalyst formulation toequilibrate for a HUT-3 seconds prior to injection into said thirdreactor, wherein said stream S4 comprises an alkyl aluminum co-catalystin said process solvent; iv) optionally, step iii) is skipped and saidin-line Ziegler-Natta catalyst formulation is formed inside said thirdreactor; wherein, said second product mixture is equilibrated for anadditional HUT-3 seconds and injected into said third reactor and saidstream S4 is independently injected into said third reactor. TypicalHold-Up-Times include: said HUT-1 is from about 5 seconds to about 70seconds, said HUT-2 is from about 2 seconds to about 50 seconds and saidHUT-3 is from about 0.5 to about 15 seconds; and said in-lineZiegler-Natta catalyst formulation and optionally said second productmixture are injected at a catalyst inlet temperature from about 20° C.to about 70° C. The in-line Ziegler-Natta catalyst formulation maycomprise: i) said magnesium compound is defined by the formula Mg(R¹)₂,wherein the R¹ groups may be the same or different; ii) said aluminumalkyl is defined by the formula Al(R³)₃, wherein the R³ groups may bethe same or different; iii) said chloride compound is defined by theformula R²Cl; iv) said metal compound is defined by the formulasM(X)_(n) or MO(X)_(n), wherein M represents titanium, zirconium,hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten,manganese, technetium, rhenium, iron, ruthenium, osmium or mixturesthereof, O represents oxygen, X represents chloride or bromide and n isan integer that satisfies the oxidation state of the metal M, and; v)said alkyl aluminum co-catalyst is defined by the formulaAl(R⁴)_(p)(OR⁵)_(q)(X)_(r), wherein the R⁴ groups may be the same ordifferent, the OR⁵ groups may be the same or different and (p+q+r)=3,with the proviso that p is greater than 0; wherein R¹, R², R³, R⁴ and R⁵represent hydrocarbyl groups having from 1 to 10 carbon atoms;optionally R² may be a hydrogen atom. The in-line Ziegler-Natta catalystformulation may comprise: a molar ratio of said aluminum alkyl to saidmagnesium compound in said third reactor from 3.0:1 to 70:1; a molarratio of said chloride compound to said magnesium compound in said thirdreactor from 1.0:1 to 4.0:1; a molar ratio of said alkyl aluminumco-catalyst to said metal compound in said third reactor from 0:1 to10:1, and; a molar ratio of said aluminum alkyl to said metal compoundin said third reactor from 0.05:1 to 2:1. In the process embodimentdescribed in this paragraph: the process solvent may be one or more C₅to C₁₂ alkanes; said first, second and third reactors may operate attemperatures from 80° C. to 300° C., and; pressures from 3 MPag to 45MPag. The process solvent in said first reactor has an average reactorresidence time from about 10 seconds to about 600 seconds and saidprocess solvent in said second reactor has an average reactor residencetime from about 10 seconds to about 720 seconds. The process may alsohave a reactor temperature difference (T^(R2)−T^(R1)) ranging from 1° C.to 120° C.; wherein T^(R2) is the temperature of the solution in saidsecond reactor and T^(R1) is the temperature of the solution in saidfirst reactor. Said optional α-olefins may be one or more of C₃ to C₁₀α-olefins. Ethylene interpolymer products may be produced employingembodiments of the solution polymerization process disclosed in thisparagraph.

Other embodiments include: a continuous solution polymerization processcomprising: i) injecting ethylene, a process solvent, a bridgedmetallocene catalyst formulation, optionally one or more α-olefins andoptionally hydrogen into a first reactor to produce a first exit streamcontaining a first ethylene interpolymer in said process solvent; ii)injecting ethylene, said process solvent, said bridged metallocenecatalyst formulation, optionally one or more α-olefins and optionallyhydrogen into a second reactor to produce a second exit streamcontaining a second ethylene interpolymer in said process solvent; iii)combining said first and said second exit streams to form a third exitstream; iv) passing said third exit stream into a third reactor andoptionally injecting into said third reactor, ethylene, process solvent,one or more α-olefins, hydrogen and a homogeneous catalyst formulationor a heterogeneous catalyst formulation to produce a fourth exit streamcontaining an optional third ethylene interpolymer, said second ethyleneinterpolymer and said first ethylene interpolymer in said processsolvent; v) phase separating said fourth exit stream to recover anethylene interpolymer product comprising said first ethyleneinterpolymer, said second ethylene interpolymer and said optional thirdethylene interpolymer; wherein, said continuous solution polymerizationprocess is improved by having one or more of the following, i.e. (a)and/or (b):

(a) at least an 70% reduced [α-olefin/ethylene] weight ratio as definedby the following formula

${\%{{Reduced}\left\lbrack \frac{\alpha - {olefin}}{{ethy}lene} \right\rbrack}} = {{100 \times \left\{ \frac{\left( \frac{\alpha - {olefin}}{{ethy}lene} \right)^{A} - \left( \frac{\alpha - {olefin}}{{ethy}lene} \right)^{C}}{\left( \frac{\alpha - {olefin}}{{ethy}lene} \right)^{C}} \right\}} \leq {{- 7}0\%}}$

wherein (α-olefin/ethylene)^(A) is calculated by dividing the weight ofsaid α-olefin added to said first reactor by the weight of said ethyleneadded to said first reactor, wherein said first ethylene interpolymerhaving a target density is produced by said bridged metallocene catalystformulation, and; (α-olefin/ethylene)^(C) is calculated by dividing theweight of said α-olefin added to said first reactor by the weight ofsaid ethylene added to said first reactor, wherein a control ethyleneinterpolymer having said target density is produced by replacing saidbridged metallocene catalyst formulation with an unbridged single sitecatalyst formulation;

(b) at least a 5% improved weight average molecular weight as defined bythe following formula

%ImprovedM_(w) = 100% × (M_(w)^(A) − M_(w)^(C))/M_(w)^(C) ≥ 5%

wherein M_(w) ^(A) is a weight average molecular weight of said firstethylene interpolymer and M_(w) ^(C) is a weight average molecularweight of a comparative ethylene interpolymer; wherein said comparativeethylene interpolymer is produced in said first reactor by replacingsaid bridged metallocene catalyst formulation with said unbridged singlesite catalyst formulation.

Additional steps of this process may comprise: a) optionally adding acatalyst deactivator A to said third exit stream, downstream of saidsecond reactor, forming a deactivated solution A; b) adding a catalystdeactivator B to said fourth exit stream, downstream of said thirdreactor, forming a deactivated solution B; with the proviso that step b)is skipped if said catalyst deactivator A is added in step a); c) phaseseparating said deactivated solution A or B to recover said ethyleneinterpolymer product. If a heterogeneous catalyst formulation was addedto the third reactor, additional process steps may comprise: d) adding apassivator to said deactivated solution A or B forming a passivatedsolution, with the proviso that step d) is skipped if said heterogeneouscatalyst formulation is not added to said third reactor, and; e) phaseseparating said deactivated solution A or B, or said passivatedsolution, to recover said ethylene interpolymer product. Ethyleneinterpolymer products may be produced employing embodiments of thesolution polymerization process disclosed in this paragraph.

Testing Methods

Prior to testing, each specimen was conditioned for at least 24 hours at23±2° C. and 50±10% relative humidity and subsequent testing wasconducted at 23±2° C. and 50±10% relative humidity. Herein, the term“ASTM conditions” refers to a laboratory that is maintained at 23±2° C.and 50±10% relative humidity; and specimens to be tested wereconditioned for at least 24 hours in this laboratory prior to testing.ASTM refers to the American Society for Testing and Materials.

Density

Ethylene interpolymer product densities were determined using ASTMD792-13 (Nov. 1, 2013).

Melt Index

Ethylene interpolymer product melt index was determined using ASTM D1238(Aug. 1, 2013). Melt indexes, I₂, I₆, I₁₀ and I₂₁ were measured at 190°C., using weights of 2.16 kg, 6.48 kg, 10 kg and a 21.6 kg respectively.Herein, the term “stress exponent” or its acronym “S.Ex.”, is defined bythe following relationship:

S.Ex. = log (I₆/I₂)/log (6480/2160)

wherein I₆ and I₂ are the melt flow rates measured at 190° C. using 6.48kg and 2.16 kg loads, respectively.

Conventional Size Exclusion Chromatography (SEC)

Ethylene interpolymer product samples (polymer) solutions (1 to 3 mg/mL)were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) androtating on a wheel for 4 hours at 150° C. in an oven. An antioxidant(2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture inorder to stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Polymer solutions were chromatographed at140° C. on a PL 220 high-temperature chromatography unit equipped withfour Shodex columns (HT803, HT804, HT805 and HT806) using TCB as themobile phase with a flow rate of 1.0 mL/minute, with a differentialrefractive index (DRI) as the concentration detector. BHT was added tothe mobile phase at a concentration of 250 ppm to protect SEC columnsfrom oxidative degradation. The sample injection volume was 200 μL. TheSEC columns were calibrated with narrow distribution polystyrenestandards. The polystyrene molecular weights were converted topolyethylene molecular weights using the Mark-Houwink equation, asdescribed in the ASTM standard test method D6474-12 (December 2012). TheSEC raw data were processed with the Cirrus GPC software, to producemolar mass averages (M_(n), M_(w), M_(z)) and molar mass distribution(e.g. Polydispersity, M_(w)/M_(n)). In the polyethylene art, a commonlyused term that is equivalent to SEC is GPC, i.e. Gel PermeationChromatography.

GPC-FTIR

Ethylene interpolymer product (polymer) solutions (2 to 4 mg/mL) wereprepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) androtating on a wheel for 4 hours at 150° C. in an oven. The antioxidant2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in orderto stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Sample solutions were chromatographed at 140°C. on a Waters GPC 150C chromatography unit equipped with four Shodexcolumns (HT803, HT804, HT805 and HT806) using TCB as the mobile phasewith a flow rate of 1.0 mL/minute, with a FTIR spectrometer and a heatedFTIR flow through cell coupled with the chromatography unit through aheated transfer line as the detection system. BHT was added to themobile phase at a concentration of 250 ppm to protect SEC columns fromoxidative degradation. The sample injection volume was 300 μL. The rawFTIR spectra were processed with OPUS FTIR software and the polymerconcentration and methyl content were calculated in real time with theChemometric Software (PLS technique) associated with the OPUS. Then thepolymer concentration and methyl content were acquired andbaseline-corrected with the Cirrus GPC software. The SEC columns werecalibrated with narrow distribution polystyrene standards. Thepolystyrene molecular weights were converted to polyethylene molecularweights using the Mark-Houwink equation, as described in the ASTMstandard test method D6474. The comonomer content was calculated basedon the polymer concentration and methyl content predicted by the PLStechnique as described in Paul J. DesLauriers, Polymer 43, pages 159-170(2002); herein incorporated by reference.

The GPC-FTIR method measures total methyl content, which includes themethyl groups located at the ends of each macromolecular chain, i.e.methyl end groups. Thus, the raw GPC-FTIR data must be corrected bysubtracting the contribution from methyl end groups. To be more clear,the raw GPC-FTIR data overestimates the amount of short chain branching(SCB) and this overestimation increases as molecular weight (M)decreases. In this disclosure, raw GPC-FTIR data was corrected using the2-methyl correction. At a given molecular weight (M), the number ofmethyl end groups (N_(E)) was calculated using the following equation;N_(E)=28000/M, and N_(E) (M dependent) was subtracted from the rawGPC-FTIR data to produce the SCB/1000C (2-Methyl Corrected) GPC-FTIRdata.

Composition Distribution Branching Index (CDBI)

The “Composition Distribution Branching Index”, hereinafter CDBI, of thedisclosed Examples and Comparative Examples were measured using aCRYSTAF/TREF 200+unit equipped with an IR detector, hereinafter theCTREF. The acronym “TREF” refers to Temperature Rising ElutionFractionation. The CTREF was supplied by PolymerChAR S.A. (ValenciaTechnology Park, Gustave Eiffel, 8, Patema, E-46980 Valencia, Spain).The CTREF was operated in the TREF mode, which generates the chemicalcomposition of the polymer sample as a function of elution temperature,the Co/Ho ratio (Copolymer/Homopolymer ratio) and the CDBI (theComposition Distribution Breadth Index), i.e. CDBI₅₀ and CDBI₂₅. Apolymer sample (80 to 100 mg) was placed into the reactor vessel of theCTREF. The reactor vessel was filled with 35 ml of1,2,4-trichlorobenzene (TCB) and the polymer was dissolved by heatingthe solution to 150° C. for 2 hours. An aliquot (1.5 mL) of the solutionwas then loaded into the CTREF column which was packed with stainlesssteel beads. The column, loaded with sample, was allowed to stabilize at110° C. for 45 minutes. The polymer was then crystallized from solution,within the column, by dropping the temperature to 30° C. at a coolingrate of 0.09° C./minute. The column was then equilibrated for 30 minutesat 30° C. The crystallized polymer was then eluted from the column withTCB flowing through the column at 0.75 mL/minute, while the column wasslowly heated from 30° C. to 120° C. at a heating rate of 0.25°C./minute. The raw CTREF data were processed using Polymer ChARsoftware, an Excel spreadsheet and CTREF software developed in-house.CDBI₅₀ was defined as the percent of polymer whose composition is within50% of the median comonomer (α-olefin) composition; CDBI₅₀ wascalculated from the composition distribution curve and the normalizedcumulative integral of the composition distribution curve, as describedin U.S. Pat. No. 5,376,439. Those skilled in the art will understandthat a calibration curve is required to convert a CTREF elutiontemperature to comonomer content, i.e. the amount of comonomer in theethylene/α-olefin polymer fraction that elutes at a specifictemperature. The generation of such calibration curves are described inthe prior art, e.g. Wild, et al., J. Polym. Sci., Part B, Polym. Phys.,Vol. 20 (3), pages 441-455: hereby fully incorporated by reference.CDBI₂₅ as calculated in a similar manner; CDBI₂₅ is defined as thepercent of polymer whose composition is with 25% of the median comonomercomposition. At the end of each sample run, the CTREF column was cleanedfor 30 minutes; specifically, with the CTREF column temperature at 160°C., TCB flowed (0.75 mL/minute) through the column for 30 minutes. CTREFdeconvolutions were performed to determine the amount of branching (BrF(#C₆/1000C)) and density of the first ethylene interpolymer using thefollowing equations: BrF (#C₆/1000C)=74.29−0.7598 (T^(P) _(CTREF)),where T^(P) _(CTREF) is the peak elution temperature of the firstethylene interpolymer in the CTREF chromatogram, and BrF(#C₆/1000C)=9341.8 (ρ¹)²−17766 (ρ¹)+8446.8, where ρ¹ was the density ofthe first ethylene interpolymer. The BrF (#C₆/1000C) and density of thesecond ethylene interpolymer was determined using blending rules, giventhe overall BrF (#C₆/1000C) and density of the ethylene interpolymerproduct. The BrF (#C₆/1000C) and density of the second and thirdethylene interpolymer was assumed to be the same.

Neutron Activation (Elemental Analysis)

Neutron Activation Analysis, hereinafter N.A.A., was used to determinecatalyst residues in ethylene interpolymer products as follows. Aradiation vial (composed of ultrapure polyethylene, 7 mL internalvolume) was filled with an ethylene interpolymer product sample and thesample weight was recorded. Using a pneumatic transfer system the samplewas placed inside a SLOWPOKE™ nuclear reactor (Atomic Energy of CanadaLimited, Ottawa, Ontario, Canada) and irradiated for 30 to 600 secondsfor short half-life elements (e.g., Ti, V, Al, Mg, and Cl) or 3 to 5hours for long half-life elements (e.g. Zr, Hf, Cr, Fe and Ni). Theaverage thermal neutron flux within the reactor was 5×10¹¹/cm²/s. Afterirradiation, samples were withdrawn from the reactor and aged, allowingthe radioactivity to decay; short half-life elements were aged for 300seconds or long half-life elements were aged for several days. Afteraging, the gamma-ray spectrum of the sample was recorded using agermanium semiconductor gamma-ray detector (Ortec model GEM55185,Advanced Measurement Technology Inc., Oak Ridge, Tenn., USA) and amultichannel analyzer (Ortec model DSPEC Pro). The amount of eachelement in the sample was calculated from the gamma-ray spectrum andrecorded in parts per million relative to the total weight of theethylene interpolymer product sample. The N.A.A. system was calibratedwith Specpure standards (1000 ppm solutions of the desired element(greater than 99% pure)). One mL of solutions (elements of interest)were pipetted onto a 15 mm×800 mm rectangular paper filter and airdried. The filter paper was then placed in a 1.4 mL polyethyleneirradiation vial and analyzed by the N.A.A. system. Standards are usedto determine the sensitivity of the N.A.A. procedure (in counts/μg).

Unsaturation

The quantity of unsaturated groups, i.e. double bonds, in an ethyleneinterpolymer product was determined according to ASTM D3124-98(published March 2011) and ASTM D6248-98 (published July 2012). Anethylene interpolymer product sample was: a) first subjected to anovernight carbon disulfide extraction to remove additives that mayinterfere with the analysis; b) the sample (pellet, film or granularform) was pressed into a plaque of uniform thickness (0.5 mm), and; c)the plaque was analyzed by FTIR to quantify the amount of terminal(vinyl) and internal unsaturation (trans-vinylene), and; d) the sampleplaque was brominated and reanalyzed by FTIR to quantify the amount ofside chain unsaturation (vinylidene). The IR resonances of these groupsappear at 908 cm⁻¹, 965 cm⁻¹ and 888 cm⁻¹, respectively. The procedureis based on Beer's Law: A=abdc, where a is the extinction coefficientfor the specific unsaturation being measured, b is the plaque thickness,d the plaque density and c the selected unsaturation. Experimentally,the weight and area of the plaque are measured rather than the densityand the thickness.

Comonomer (α-Olefin) Content: Fourier Transform Infrared (FTIR)Spectroscopy

The quantity of comonomer in an ethylene interpolymer product wasdetermine by FTIR and reported as the Short Chain Branching (SCB)content having dimensions of CH₃#/1000C (number of methyl branches per1000 carbon atoms). This test was completed according to ASTM D6645-01(2001), employing a compression molded polymer plaque and aThermo-Nicolet 750 Magna-IR Spectrophotometer. The polymer plaque wasprepared using a compression molding device (Wabash-Genesis Seriespress) according to ASTM D4703-16 (April 2016).

Linear Melt Rheology

Oscillatory shear measurements under small strain-amplitudes werecarried out to obtain linear viscoelastic functions at 190° C. under N₂atmosphere, at a strain amplitude of 10% and over a frequency range of0.02-126 rad/s at 5 points per decade. Frequency sweep experiments wereperformed with a TA Instruments DHR3 stress-controlled rheometer using acone-plate geometry with a cone angle of 5°, a truncation of 137 μm anda diameter of 25 mm. In this experiment a sinusoidal strain-wave wasapplied and the stress-wave response was analyzed in terms of linearviscoelastic functions; i.e. complex viscosity, complex modulus, etc.The zero-shear rate viscosity (η₀) based on the linear regime frequencysweep results was predicted by Ellis model (see R. B. Bird et al.“Dynamics of Polymer Liquids. Volume 1: Fluid Mechanics”Wiley-Interscience Publications (1987) p. 228) or Carreau-Yasuda model(see K. Yasuda (1979) PhD Thesis, IT Cambridge). In this disclosure theonset of shear thinning, τ (s⁻¹), was determined by fitting the threeparameter Ellis model (η₀, τ and n) to the magnitude of complexviscosity (|η*|) versus angular frequency (ω) data at 190° C.; i.e.|η*|=η₀/(1+(ω/τ)_((n-1)).

The Flow Activation Energy (FAE) having dimensions of kJ/mol was alsodetermined. The Anton Paar MCR501 rotational rheometer was used togenerate the data from which the FAE was calculated; specifically, themelt-state complex viscosity versus angular frequency in a linear regime(from 0.05 to 100 rad/s at 7 data points per decade at astrain-amplitude of 5%) at four different temperatures (160, 175, 190and 205° C.) were measured. Using 190° C. as the reference temperature,a time-temperature-superposition shift was carried out to obtain theshift factors. The FAE of each sample was calculated using TTS(time-temperature superposition) shifting of the complex viscositycurves and Arrhenius equation fitting on horizontal shift factors ofeach temperature with RheoPlus and Orchestrator software (see Markovitz,H., “Superposition in Rheology”, J. Polym. Sci., Polymer SymposiumSeries 50, 431-456 1975).

Nonlinear Melt Rheology

Nonlinear melt rheology was measured at 190° C. under nitrogenatmosphere, at an angular frequency of 0.1 rad/s, at a strain-amplituderange of 1 and 1000% and at a gap-size of 1 mm using a 25 mm stainlessparallel-plate geometry. Multiple gap-size measurements indicated thatthese test conditions can generate a nearly instability-free stresssignal suitable for further analysis. In this disclosure, thedisentanglement kinetics of PE melts under a strong oscillatory shearflow was studied towards developing a very sensitive, MW- andMWD-independent intracycle nonlinear viscoelasticity parameter capableof detecting presence of LCB species in ethylene/alpha-olefininterpolymers. The intracycle nonlinear function, INF (dimensionless),was determined experimentally for linear or long-chain branched ethyleneinterpolymers according to Journal of Rheology 2008, 52, pp 1427-1458using RheoCompass 1.17 software.

The LCB characterization method described in this disclosure, mainlyrelies on a nonlinear rheology method amplifying subtle differences inthe kinetics of entanglements dissociation in the melt-state in linearand LCB ethylene interpolymer compositions under a strong oscillatoryshear-field. The following is a step-by-step procedure enabling askilled technician in the area of rheological testing and rheologicaldata analysis to complete the test and determine presence of long chainbranched structures in an ethylene interpolymer product.

Step 1

A pre-compression molded disk of the ethylene interpolymer with athickness of about 1.9-2 mm is loaded on the rheometer lower plate at atemperature close to 190° C. After reaching thermal equilibrium at 190°C., the upper plate is lowered squeezing the molten polymer at a rate of1000 to 100 μm/s not exceeding a normal force of 40 N. The upper plateis lowered to a vertical position 30 μm above the testing gap-height andthe excess molten sample is trimmed and the gap is lowered to thetesting position of 1 mm. The temperature is then kept constant to reachthermal equilibrium at 190±0.1° C. The melt-state sample is thensubjected to an oscillating strain-wave at a fixed angular frequency andtemperature with a step-wise increasing strain-amplitude from a lowerlimit strain-amplitude to an upper limit strain-amplitude to obtain astress-wave response and corresponding viscous Lissajous-Bowditch loop(i.e. stress versus strain-rate loops; the insets in FIGS. 3 and 4 ) ateach strain-amplitude level. Twenty-two equidistantly spacedstrain-amplitude values within the range of 1 to 1000% were applied atan angular frequency of 0.1 rad/s.

Step 2

The Intracycle nonlinear function, INF, is determined experimentallyusing the instantaneous dynamic viscosities at maximum strain-rate(η′_(L)) and at minimum strain-rate (η′_(M)) in the viscousLissajous-Bowditch loop at each strain-amplitude level using

${INF} = \frac{\eta_{L}^{\prime} - \eta_{M}^{\prime}}{\eta_{L}^{\prime}}$(INF is dimensionless) by a rheology data processing software (AntonPaar RheoCompass 1.17 in this disclosure). The instantaneous dynamicviscosities at maximum strain-rate (η′_(L)) and at minimum strain-rate(η′_(M)) in a viscous Lissajous-Bowditch loop at a certainstrain-amplitude level can be obtained by the stress decompositionmethod introduced in Journal of rheology 2005, 49, pp 747-758 and byfitting the Chebyshev polynomials of the first kind to the viscousstress response of tested linear or long-chain branched ethyleneinterpolymers as described in Journal of Rheology 2008, 52, pp1427-1458. In the insets in FIGS. 3 and 4 , the obtained instantaneousdynamic viscosities at maximum strain-rate (η′_(L)) and at minimumstrain-rate (η′_(M)) are visualized as the slope of a secant linecrossing the viscous Lissajous-Bowditch loop at the maximum strain-rateand the slope of a tangent line touching the viscous Lissajous-Bowditchloop at a strain-rate of zero for Comparative example 5a and Inventiveexample 1, respectively. INF is a material function that is initiallyzero (within the linear regime) and then changes its sign to positive(intracycle shear-thickening) and/or negative values (intracycleshear-thinning) as strain amplitude increases and a nonlinear responseemerges. A dimensionless scaling function, similar to Journal ofRheology 2010, 54, pp 27-63, can be defined as ζ=γ₀ cos δ_(a) _(M) _(ω)where γ₀ is the imposed strain-amplitude and δ_(a) _(M) _(ω) is thephase-angle at a frequency of a_(M)ω=0.1 rad/s, wherein a_(M) is thetime-molecular weight superposition shift factor described below (seeFIG. 2 ), was further applied to remove the effect of linearviscoelasticity and molecular weight.Step 3

Further, in the third step, the INF obtained for the ethyleneinterpolymer product of interest is compared with a reference INFpredicted for a linear (non-long chain branched) ethylene interpolymerproduct having a polydispersity equivalent to the said ethyleneinterpolymer product. Polydispersity of a given ethylene interpolymerproduct can be characterized using any combination of moments ofmolecular weight distribution; i.e. number-average molecular weight,weight-average molecular weight, z-average molecular weight,(z+1)-average molecular weight, etc. In this disclosure, the ratio ofz-average molecular weight divided by weight-average molecular weightwas preferably used as a measure of polydispersity. The importance of

$\frac{M_{z}}{M_{w}}$has been extensively proposed in rheology literature (e.g. see Polym,Eng. Sci. 1996 36, pp 852-861).

As shown in FIG. 3 , the reference INF for a linear ethyleneinterpolymer can be predicted using Eq.1 as follows (INF isdimensionless):

$\begin{matrix}{{{INF}^{lin} = {{- K}{\zeta^{1.45}\left( {\zeta^{a} - C^{*}} \right)}}};{\zeta = {\gamma_{0}\cos\delta_{a_{M}\omega}}}} & \left( {{Eq}.1} \right)\end{matrix}$

in which K is a constant equal 0.3722, γ₀ is the imposed strainamplitude, a_(M) is the time-molecular weight superposition shift factordefined as

$\left( \frac{M_{w}}{M_{ref}} \right)^{3.41}$where M_(w) is the SEC weight-average molecular weight and M_(ref) is areference molecular weight of 10⁵ g/mol. In Eq.1, δ_(a) _(M) _(ω) is thephase-angle at a frequency of a_(M)ω=0.1 rad/s. FIG. 2 schematicallydisplays the procedure used for interpolating the cosine of phase angleat a weighted frequency of a_(M)ω=0.1 rad/s for non-limiting examples ofExample 1 and Comparatives T3, R2 and S2 using a 33-mode generalizedMaxwell model (see Li et al. ANTEC 2014). It should be added that δ_(a)_(M) _(ω) values larger than 88.5° were not used for these calculationsand were replaced by the largest phase angle measured within a frequencyrange of 0.05-100 rad/s. Parameters a* and C* in Eq.1 were defined as afunction of the SEC-determined weight-average molecular weight M_(w) andz-average molecular weight M_(z) as follows:

$\begin{matrix}{a^{*} = {{f\left( \frac{M_{z}}{M_{w}} \right)} = \left\{ \begin{matrix}0 & {\frac{M_{z}}{M_{w}} \leq {{1.6}4}} \\{{0.8645\ \left( {\frac{M_{z}}{M_{w}} - {1.5}} \right)} - {{0.1}198}} & {1.64 < \frac{M_{z}}{M_{w}} < {{2.2}1}} \\{{0.5938\left( {\frac{M_{z}}{M_{w}} - {1.5}} \right)^{2}} - {{1.1}803\left( {\frac{M_{z}}{M_{w}} - {1.5}} \right)} + {{1.0}455}} & {\frac{M_{z}}{M_{w}} \geq {{2.2}1}}\end{matrix} \right.}} & \left( {{Eq}\text{.2}} \right)\end{matrix}$ $\begin{matrix}{C^{*} = {{g\left( \frac{M_{z}}{M_{w}} \right)} = \left\{ \begin{matrix}0 & {\frac{M_{z}}{M_{w}} < {{2.2}1}} \\{{{0.5}944\ {\ln\left( {\frac{M_{z}}{M_{w}} - {1.5}} \right)}} + {{0.2}057}} & {\frac{M_{z}}{M_{w}} \geq {{2.2}1}}\end{matrix} \right.}} & \left( {{Eq}\text{.3}} \right)\end{matrix}$Step 4

In the fourth step, presence of LCB in the ethylene interpolymer productof interest is detected according to a positive deviation from thepredicted reference INF. The measured INF values of LCB ethyleneinterpolymers obtained at 190° C. at an angular frequency of 0.1 rad/sover a strain amplitude range of 1-10³%, as shown by the solid line inFIG. 4 , can be described using the following formula (INF isdimensionless):

$\begin{matrix}{{{INF} = {{- K}{\zeta^{1.45}\left( {\zeta^{a} - C} \right)}}};{\zeta = {\gamma_{0}\cos\delta_{a_{M}\omega}}}} & \left( {{Eq}\text{.4}} \right)\end{matrix}$

in which K is a constant equal 0.3722 and γ₀, a_(M) and δ_(a) _(M) _(ω)parameters have the same definition as in Eq.1. Parameters a and C inEq. 4 were used as fitted constants by minimizing sum of squaredresiduals for data point with at least 0.1% nonlinearity (i.e. athird-order harmonic ratio I_(3/1) of 0.001) to describe differentexperimental intracycle viscous nonlinear behaviors ranging from anintracycle shear-thinning (INF<0) behavior to an intracycleshear-thickening behavior (INF>0).

One can then calculate the ‘network parameter’, Δ_(int.), which purelyreflects the impact of branching content on the intracycle nonlinearfunction, INF; according to the integrated area between the measured INFand INF^(lin) over an ζ interval of 0.01 to 0.7 as follows:

$\begin{matrix}{\Delta_{{int}.} = {{\int_{{0.0}1}^{0.7}{\left\lbrack {{INF} - {INF}^{lin}} \right\rbrack d\zeta}} = {\left\lbrack {{\frac{- K}{a + 1.45}\zeta^{a + 2.45}} + {\frac{KC}{2.45}\zeta^{2.45}} + \left. {{\frac{K}{a^{*} + 245}\zeta^{a^{*} + 2.45}} - {\frac{{KC}^{*}}{2.45}\zeta^{2.45}}} \right\rbrack_{{0.0}1}^{0.7}} \right.}}} & \left( {{Eq}.5} \right)\end{matrix}$Melt Strength

The Accelerated-Haul-Off (AHO) Melt Strength (MS), having dimensions ofcenti-Newtons (cN), was measured on a Rosand RH-7 capillary rheometer(available from Malvern Instruments Ltd, Worcestershire, UK) having abarrel diameter of 15 mm, a flat die of 2-mm diameter and L/D ratio of10:1 and equipped with a pressure transducer of 10,000 psi (68.95 MPa).The polymer melt was extruded through a capillary die under a constantrate (constant piston speed of 5.33 mm/min at 190° C.) which formed anextruded polymer filament. The polymer filament was then passed througha set of rollers and stretched at an ever-increasing haul-off speeduntil rupture. More specifically, the initial polymer filament speed wasincreased from 0 m/min at a constant acceleration rate from 50 to 80m/min² until the polymer filament ruptured. During this experiment, theforce on the rollers was constantly measured, initially the force risesquickly and then plateaus prior to filament rupture. The mean value ofthe force in the plateau region of the force versus time curve wasdefined as the melt strength for the polymer, measured in centi-Newtons(cN).

Vicat Softening Point (Temperature)

The Vicat softening point of an ethylene interpolymer product wasdetermined according to ASTM D1525-07 (published December 2009). Thistest determines the temperature at which a specified needle penetrationoccurs when samples are subjected to ASTM D1525-07 test conditions, i.e.heating Rate B (120±10° C./hr and 938 gram load (10±0.2N load).

Heat Deflection Temperature

The heat deflection temperature of an ethylene interpolymer product wasdetermined using ASTM D648-07 (approved Mar. 1, 2007). The heatdeflection temperature is the temperature at which a deflection toolapplying 0.455 MPa (66 PSI) stress on the center of a molded ethyleneinterpolymer plaque (3.175 mm (0.125 in) thick) causes it to deflect0.25 mm (0.010 in) as the plaque is heated in a medium at a constantrate.

Flexural Properties

The flexural properties, i.e. flexural secant and tangent modulus andflexural strength were determined using ASTM D790-10 (published in April2010).

Film Dart Impact

Film dart impact strength was determined using ASTM D1709-09 Method A(May 1, 2009). In this disclosure the dart impact test employed a 1.5inch (38 mm) diameter hemispherical headed dart.

Film Puncture

Film “puncture”, the energy (J/mm) required to break the film wasdetermined using ASTM D5748-95 (originally adopted in 1995, reapprovedin 2012).

Film Lub-Tef Puncture

The ‘Lub-Tef Puncture’ test was performed using a specifically designedTeflon probe at a 20 in/min. puncture rate, the purpose of this test wasto determine the puncture resistance of monolayer ethylene interpolymerproduct films. An MTS Insight/Instron Model 5 SL Universal TestingMachine equipped with MTS Testworks 4 software was used; MTS 1000 N or5000 N load cells were used. Film samples were ASTM conditioned for atleast 24 hours prior to testing. Given a roll of blown film, 4.25 inchsample were cut in the transverse direction, having a length of the filmroll layflat dimension and the outside of the film is labelled (theprobe impacts the outside of the film). Mount the Teflon coated punctureprobe and set the testing speed to 20 inch/min. Mount the film sampleinto the clamp and deposit 1 cm³ of lube onto the center of the film.When the crosshead is in the starting test position, set the limitswitches on the Load Cell frame to 10 inch below and above thecrosshead. Measure and record film sample thickness and begin (start)the puncture test. Prior to the next test thoroughly clean the probehead. Repeat until at least 5 consistent puncture results are obtained,i.e. standard deviation less than 10%. The lubricant used was MukoLubricating Jelly; a water-soluble personal lubricant available fromCardinal Health Inc., 1000 Tesma Way, Vaughan, ON L4K 5R8 Canada. Theprobe head was machined Teflon having a 1.4 inch cone shape with a flattip.

Film Tensile Properties

The following film tensile properties were determined using ASTM D882-12(Aug. 1, 2012): tensile break strength (MPa), elongation at break (%),tensile yield strength (MPa) and tensile elongation at yield (%).Tensile properties were measured in the both the machine direction (MD)and the transverse direction (TD) of the blown films.

Film Secant Modulus

The secant modulus is a measure of film stiffness. Secant moduli weredetermined according to ASTM D882. The secant modulus is the slope of aline drawn between two points on the stress-strain curve, i.e. thesecant line. The first point on the stress-strain curve is the origin,i.e. the point that corresponds to the origin (the point of zero percentstrain and zero stress), and; the second point on the stress-straincurve is the point that corresponds to a strain of 1%; given these twopoints the 1% secant modulus is calculated and is expressed in terms offorce per unit area (MPa). The 2% secant modulus is calculatedsimilarly. This method is used to calculated film modulus because thestress-strain relationship of polyethylene does not follow Hook's law;i.e. the stress-strain behavior of polyethylene is non-linear due to itsviscoelastic nature. Secant moduli were measured using a conventionalInstron tensile tester equipped with a 200 lbf load cell. Strips ofmonolayer film samples were cut for testing with following dimensions:14 inches long, 1 inch wide and 1 mil thick; ensuring that there were nonicks or cuts on the edges of the samples. Film samples were cut in boththe machine direction (MD) and the transverse direction (TD) and tested.ASTM conditions were used to condition the samples. The thickness ofeach film was accurately measured with a hand-held micrometer andentered along with the sample name into the Instron software. Sampleswere loaded in the Instron with a grip separation of 10 inch and pulledat a rate of 1 inch/min generating the strain-strain curve. The 1% and2% secant modulus were calculated using the Instron software.

Film Elmendorf Tear

Film tear performance was determined by ASTM D1922-09 (May 1, 2009); anequivalent term for tear is “Elmendorf tear”. Film tear was measured inboth the machine direction (MD) and the transverse direction (TD) of theblown films.

Film Puncture-Propagation Tear

Puncture-propagation tear resistance of blown film was determined usingASTM D2582-09 (May 1, 2009). This test measures the resistance of ablown film to snagging, or more precisely, to dynamic puncture andpropagation of that puncture resulting in a tear. Puncture-propagationtear resistance was measured in the machine direction (MD) and thetransverse direction (TD) of the blown films.

Film Opticals

Film optical properties were measured as follows: Haze, ASTM D1003-13(Nov. 15, 2013), and Gloss ASTM D2457-13 (Apr. 1, 2013).

Film Dynatup Impact

Instrumented impact testing was carried out on a machine called aDynatup Impact Tester purchased from Illinois Test Works Inc., SantaBarbara, Calif., USA; those skilled in the art frequently call this testthe Dynatup impact test. Testing was completed according to thefollowing procedure. Test samples are prepared by cutting 5 inch (12.7cm) wide and 6 inch (15.2 cm) long strips from a roll of blown film;film was 1 mil thick. Prior to testing, the thickness of each sample wasaccurately measured with a handheld micrometer and recorded. ASTMconditions were employed. Test samples were mounted in the 9250 DynatupImpact drop tower/test machine using the pneumatic clamp. Dynatup tup#1, 0.5 inch (1.3 cm) diameter, was attached to the crosshead using theAllen bolt supplied. Prior to testing, the crosshead is raised to aheight such that the film impact velocity is 10.9±0.1 ft/s. A weight wasadded to the crosshead such that: 1) the crosshead slowdown, or tupslowdown, was no more than 20% from the beginning of the test to thepoint of peak load and 2) the tup must penetrate through the specimen.If the tup does not penetrate through the film, additional weight isadded to the crosshead to increase the striking velocity. During eachtest the Dynatup Impulse Data Acquisition System Software collected theexperimental data (load (lb) versus time). At least 5 film samples aretested and the software reports the following average values: “DynatupMaximum (Max) Load (lb)”, the highest load measured during the impacttest; “Dynatup Total Energy (ft-lb)”, the area under the load curve fromthe start of the test to the end of the test (puncture of the sample),and; “Dynatup Total Energy at Max Load (ft-lb)”, the area under the loadcurve from the start of the test to the maximum load point.

Cold Seal Strength

The cold seal strength of 3.5 mil (88.9 μm) 9-layer films were measuredusing a conventional Instron Tensile Tester. In this test, twomultilayer films were sealed (layer 1 to layer 1) over a range oftemperatures, the seals were then aged at least 24 hours at 73° F. (23°C.) and prior to tensile testing. The following parameters were used inthe Cold Seal Strength Test: the film specimen width was 1 inch (25.4mm); film sealing time, 0.5 second; film sealing pressure, 0.27 N/mm²;temperature range, 90° C. to 170° C. with temperature increments of 5 or10° C. After aging, seal strength was determined using the followingtensile parameters: pull (crosshead) speed, 12 in/min (30.48 cm/min);grip separation 0.39 in (0.99 cm); direction of pull, 90° to seal; and 4to 8 samples of each multilayer film were tested at each temperatureincrement to calculate an average value. In the cold seal test, the SealInitiation Temperature (SIT) was recorded, in ° C.; the SIT was thetemperature at which the seal strength reached 8.8 N/in.

Film Hot Tack Strength

The hot tack strength of 3.5 mil (88.9 μm) 9-layer films were measuredusing a J&B Hot Tack Tester (commercially available from Jbi Hot Tack,Geloeslaan 30, B-3630 Maamechelen, Belgium). In the hot tack test thestrength of a polymer to polymer seal is measured immediately after heatsealing two films together, i.e., when the polyolefin is in asemi-molten state. This test simulates heat sealing on automaticpackaging machines, e.g., vertical or horizontal form, fill and sealequipment. The following parameters were used in the J&B Hot Tack Test:film specimen width, 1 inch (25.4 mm); film sealing time, 0.5 second;film sealing pressure, 0.27 N/mm²; seal time, 0.5 s, cool time, 0.5second; film peel speed, 7.9 in/second (200 mm/second); temperaturerange, 90° C. to 170° C.; temperature increments of 5 or 10° C.; and 4to 8 samples of each multilayer film were tested at each temperatureincrement to calculate an average value. In this disclosure, the HotTack Onset (HTO) temperature, measured in ° C., was the temperature atwhich the hot tack force reached 1N. In addition, the Maximum Hot TackForce (Max. HTF) was recorded, i.e. the maximum hot tack force (N)recorded during the hot tack experiment; as was the temperature (° C.)at which the Max. HTF was observed.

Film Hexane Extractables

Hexane extractables was determined according to the Code of FederalRegistration 21 CFR § 177.1520 Para (c) 3.1 and 3.2; wherein thequantity of hexane extractable material in a film is determinedgravimetrically. Elaborating, 2.5 grams of 3.5 mil (89 μm) monolayerfilm was placed in a stainless steel basket, the film and basket wereweighed (w^(i)). While in the basket the film was: extracted withn-hexane at 49.5° C. for two hours; dried at 80° C. in a vacuum oven for2 hours; cooled in a desiccator for 30 minutes, and; weighed (w^(f)).The percent loss in weight is the percent hexane extractables (w^(C6)):w^(C6)=100×(w^(i)−w^(f))/w^(i).

EXAMPLES

Pilot Plant Polymerizations

The following examples are presented for the purpose of illustratingselected embodiments of this disclosure, it being understood that, theexamples presented hereinafter do not limit the claims presented.Examples of ethylene interpolymer products were prepared in a continuoussolution process pilot plant as described below.

Solution process conditions for Examples 1-3 are summarized in Tables 4Aand 4B. Two CSTR reactors (R1 and R2), configured in series, wereemployed to manufacture Examples 1 and 2. One CSTR reactor was employedto manufacture Example 3 (R2). R1 pressure varied from 14 MPa to 18 MPa;R2 was operated at a lower pressure to facilitate continuous flow fromR1 to R2. CSTR's were agitated to give conditions in which the reactorcontents were well mixed. The process was operated continuously byfeeding fresh process solvent, ethylene, 1-octene and hydrogen to thereactors. Methylpentane was used as the process solvent (a commercialblend of methylpentane isomers). The volume of the first CSTR reactor(R1) was 3.2 gallons (12 L), the volume of the second CSTR reactor (R2)was 5.8 gallons (22 L) and the volume of the tubular reactor (R3) was0.58 gallons (2.2 L).

The following components were used to prepare the bridged metallocenecatalyst formulation: component A,diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl, [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] (abbreviated CpF-2); component M,methylaluminoxane (MMAO-07); component B, trityltetrakis(pentafluoro-phenyl)borate, and; component P,2,6-di-tert-butyl-4-ethylphenol. The following catalyst componentsolvents were used: methylpentane for components M and P, and; xylenefor component A and B.

Comparative ethylene interpolymer products were manufactured using theunbridged single site catalyst formulation comprising: component C,cyclopentadienyl tri(tertiary butyl)phosphinimine titanium dichloride[Cp[(t-Bu)₃PN]TiCl₂] (abbreviated PIC-1); component M, methylaluminoxane(MMAO-07); component B, trityl tetrakis(pentafluoro-phenyl)borate, and;component P, 2,6-di-tert-butyl-4-ethylphenol. The following catalystcomponent solvents were used: methylpentane for components M and P, and;xylene for component A and B.

In the case of Example 1, Table 4A shows the quantity of CpF-2 inreactor 1 (R1) was 0.85 ppm, i.e. ‘R1 catalyst (ppm)’. The efficiency ofthe bridged metallocene catalyst formulation was optimized by adjustingthe mole ratios of the catalyst components and the R1 catalyst inlettemperature. As shown in Table 4A, the mole ratios optimized were:([M]/[A]), i.e. [(MMAO-07)/(CpF-2)]; ([P]/[M]), i.e.[(2,6-di-tert-butyl-4-ethylphenol)/(MMAO-07)], and; ([B]/[A]), i.e.[(trityl tetrakis(pentafluoro-phenyl)borate)/(CpF-2)]. To be more clear,in Example 1 (Table 4A), the mole ratios in R1 were: R1 ([M]/[A])=50; R1([P]/[M])=0.40, and; R1 ([B]/[A])=1.2. As shown in Table 4B, the R1catalyst inlet temperature was 21° C. in the case of Example 1. InExamples 1 and 2 a second bridged metallocene catalyst formulation wasinjected into the second reactor (R2). Tables 4A and 4B discloseadditional process parameters, e.g. ethylene and 1-octene splits betweenthe reactors, and reactor temperatures and ethylene conversions, etc.

Average residence time of the solvent in a reactor is primarilyinfluenced by the amount of solvent flowing through each reactor and thetotal amount of solvent flowing through the solution process, thefollowing are representative or typical values for the Examples shown inTables 4A and 4B: average reactor residence times were: 61 seconds inR1, 73 seconds in R2, 7.3 seconds for an R3 volume of 0.58 gallons (2.2L).

Polymerization in the continuous solution polymerization process wasterminated by adding a catalyst deactivator to the third exit streamexiting the tubular reactor (R3). The catalyst deactivator used wasoctanoic acid (caprylic acid), commercially available from P&GChemicals, Cincinnati, Ohio, U.S.A. The catalyst deactivator was addedsuch that the moles of fatty acid added were 50% of the total molaramount of catalytic metal and aluminum added to the polymerizationprocess.

A two-stage devolitizing process was employed to recover the ethyleneinterpolymer product from the process solvent, i.e. two vapor/liquidseparators were used and the second bottom stream (from the second V/Lseparator) was passed through a gear pump/pelletizer combination.

Prior to pelletization the ethylene interpolymer product was stabilizedby adding 500 ppm of Irganox 1076 (a primary antioxidant) and 500 ppm ofIrgafos 168 (a secondary antioxidant), based on weight of the ethyleneinterpolymer product. Antioxidants were dissolved in process solvent andadded between the first and second V/L separators.

Ethylene Interpolymer product Examples 1-3 were characterized and theresults are disclosed in Table 5A. Table 5A also discloses Examples 4-6prepared on the same solution pilot plant employing the bridgedmetallocene catalyst formulation and reactor configuration as describedabove for Examples 1-3. In Table 5A the term ‘FAE (J/mol)’ was the FlowActivation Energy of Examples 1-6 determined as described in theexperimental section; ‘MS (cN)’ was the Melt Strength, and; ‘τ(s⁻¹)’discloses the rheological onset of shear-thinning.

Table 5B characterizes comparative ethylene interpolymer products.Comparative 1a was SURPASS FPs117-C, Comparative 2a was produced in thesolution pilot plant using a bridged metallocene catalyst formulation inthe first reactor and an unbridged single site catalyst formulation inthe second reactor, Comparative 3a was produced in the solution pilotplant using a bridged metallocene catalyst formulation in the firstreactor and an in-line Ziegler-Natta catalyst formulation in the secondreactor, Comparative 4a was SURPASS VPsK914, Comparative 5a was SCLAIRFP120 and Comparatives 14-16 were was produced in the solution pilotplant employing an unbridged single site catalyst formulation inreactors 1 and 2.

Table 5C characterizes additional comparative ethylene interpolymerproducts. Comparatives Q1-Q4 were Queo products, specifically Queo 0201,Queo 8201, Queo 0203 and Queo 1001, respectively. The remainingcomparative samples were: Comparative R1 was Affinity PL1880;Comparative S1 was Enable 20-05HH; Comparative T1 was Exceed 1018CA;Comparative U1 was Elite AT 6202, and; Comparative V1 was Elite 5401G.

There is a need to improve the continuous solution polymerizationprocess, e.g. to increase the production rate, where production rate isthe kilograms of ethylene interpolymer product produced per hour. Tables6A and 6B disclose series dual reactor solution polymerization processconditions that produced products having melt indexes (I₂) of about 1.0dg/min and densities of about 0.9175 g/cc. An improved continuoussolution polymerization process is represented by Example 6 in Table 6A.Example 6 was an ethylene interpolymer product produced on the solutionpilot plant (described above) by injecting the bridged metallocenecatalyst formulation (CpF-2) into reactors 1 and 2.

A comparative continuous solution polymerization process is representedby Comparative 8 in Table 6A. Comparative 8 was a comparative ethyleneinterpolymer product produced on the same solution pilot plant byinjecting the unbridged single site catalyst formulation (PIC-1) intoreactors 1 and 2. The improved process had a production rate, PR^(A), of93.0 kg/hr; in contrast the comparative process had a comparativeproduction rate, PR^(C), of 81.3 kg/hr. The improved process had anincreased production rate, PR^(I), of 14.5%, i.e.

PR^(I) = 100 × (PR^(A) − PR^(C))/PR^(C) = 100 × ((93. − 81.3)/81.3) = 14.5%.

Tables 7A and 7B disclose series dual reactor solution polymerizationprocess conditions that produced products having fractional melt indexes(I₂) of about 0.8 dg/min and densities of about 0.9145 g/cc. Example 5was synthesized using the bridged metallocene catalyst formulation; incontrast, Comparative 9 was synthesized using the unbridged single sitecatalyst formulation. In the case of Example 5, the improved continuoussolution polymerization process had a production rate, PR^(A), of 93.9kg/hr; in contrast the comparative process had a comparative productionrate, PR^(C), of 79.4 kg/hr. The improved process had an increasedproduction rate, PR^(I), of 18.3%.

There is a need to improve the continuous solution polymerizationprocess, e.g. to increase the molecular weight of the ethyleneinterpolymer product produced at a specific reactor temperature. Inaddition, in solution polymerization there is a need for catalystformulations that efficiently incorporate α-olefins into the propagatingmacromolecular chain. Expressed alternatively, there is a need forcatalyst formulations that produce an ethylene interpolymer product,having a specific density, at a lower (α-olefin/ethylene) ratio in thereactor.

Table 8 compares the solution polymerization conditions of Example 10manufactured using a bridged metallocene catalyst formulation (CpF-2)and Comparative 10s simulated using an unbridged single site catalystformulation (PIC-1). Example 10 was produced on the continuous solutionprocess pilot plant (described above) employing one CSTR reactor.Relative to Example 10, Comparative 10s was computer simulated using thesame reactor configuration, same reactor temperature (165° C.), samehydrogen concentration (4 ppm), same ethylene conversion (90% (Q^(T)))and the [α-olefin/ethylene] ratio was adjusted to produce an ethyleneinterpolymer product having the same branch frequency as Example 10(about 16 C₆/1000C). Given Table 8 it is evident that Example 10characterizes an improved solution polymerization process, relative toComparative 10s, i.e. an improved ‘% Reduced [α-olefin/ethylene]’ ratioresults. Elaborating, the [α-olefin/ethylene]^(A) weight ratio ofExample 10 was 83.8% lower (improved) relative to the[α-olefin/ethylene]^(C) weight ratio of Comparative 10s, i.e.:

${{\%{{Reduced}\left\lbrack \frac{\alpha - {olefin}}{ethylene} \right\rbrack}} = {100 \times \left\{ \frac{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{A} - \left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}}{\left( \frac{\alpha - {olefin}}{ethylene} \right)^{C}} \right\}}}{{\%{{Reduced}\left\lbrack \frac{\alpha - {olefin}}{ethylene} \right\rbrack}} = {{100 \times \left\{ \frac{{{0.1}7} - {{1.0}5}}{{1.0}5} \right\}} = {{- 8}3.8\%}}}$

where the superscript^(A) represents catalyst Component A (Formula (I))and the superscript^(C) represents catalyst Component C (Formula (II)).In addition, the bridged metallocene catalyst formulation produced a ‘%Improved M_(w)’. Elaborating, the weight average molecular weight ofExample 10 (M_(w) ^(A)) was 73.6% higher (improved), relative to theweight average molecular weight of Comparative 10s (M_(w) ^(C)), i.e.:

%ImprovedM_(w) = 100 × (M_(w)^(A) − M_(w)^(C))/M_(w)^(C)%ImprovedM_(w) = 100 × (82720 − 47655)/47655 = 73.6%.

Similarly, Table 8 also compares the solution polymerization conditionsof Example 11 manufactured using the bridged metallocene catalystformulation (CpF-2) with simulated Comparative 10s using the unbridgedsingle site catalyst formulation (PIC-1). Example 11 and Comparative 11swere manufactured or simulated, respectively, using the same reactorconfiguration, same reactor temperature (165° C.), same hydrogenconcentration (6 ppm), same ethylene conversion (85% (Q^(T))) and therespective [α-olefin/ethylene] ratio was adjusted to produce ethyleneinterpolymer products having about the same branch frequency (about 21.5C₆/1000C). The [α-olefin/ethylene]^(A) weight ratio of Example 11 was72.7% lower (improved) relative to the [α-olefin/ethylene]^(C) ofComparative 11s. In addition, the weight average molecular weight ofExample 11 (M_(w) ^(A)) was 199% higher (improved), relative to theweight average molecular weight of Comparative 11s (M_(w) ^(C)), asshown in Table 8.

Table 9 summarizes solution polymerization process data at higher andlower reactor temperatures, relative to Table 8. For example, at 190° C.reactor temperature, Example 12 can be compared with simulatedComparative 12s. The [α-olefin/ethylene]^(A) weight ratio of Example 12was 90.8% lower (improved) relative to the [α-olefin/ethylene]^(C)weight ratio of Comparative 12s. In addition, the weight averagemolecular weight of Example 12 (M_(w) ^(A)) was 70.4% higher (improved),relative to the weight average molecular weight of Comparative 12s(M_(w) ^(C)), as shown in Table 9.

In Table 9, Example 13 can be compared with simulated Comparative 13s,both at reactor temperatures of 143° C. The [α-olefin/ethylene]^(A)weight ratio of Example 13 was 88.9% lower (improved) relative to the[α-olefin/ethylene]^(C) of Comparative 13s and the weight averagemolecular weight of Example 13 (M_(w) ^(A)) was 182% higher (improved)relative to the weight average molecular weight of Comparative 13s(M_(w) ^(C)).

Tables 10A and 10B compare dual reactor solution polymerizationconditions of Example 14 and Comparative 14. Table 10A discloses reactor1 process conditions and Table 10B discloses reactor 2 processconditions. Example 14 was a dual reactor ethylene interpolymer productcontaining a first ethylene interpolymer synthesized using a bridgedmetallocene catalyst formulation and a second ethylene interpolymersynthesized using an unbridged single site catalyst. Comparative 14 wasa comparative dual reactor ethylene interpolymer product where both thefirst and second ethylene interpolymers were synthesized using anunbridged single site catalyst. Table 10A shows reactor temperatures(118.7° C.±0.7%) and ethylene conversions (80.0%) were the same forExample 14 and Comparative 14; however, in the case of the bridgedmetallocene catalyst formulation an 87.3% lower (α-olefin/ethylene)weight fraction was employed in the first reactor, i.e. a 0.35 weightfraction, relative to the unbridged single site catalyst formulation,i.e. 2.76 weight fraction. In addition, the amount of hydrogen employedin reactor 1 was 3-fold higher when using the bridged metallocenecatalyst formulation relative to the unbridged single site catalystformulation. Those of ordinary experience are cognizant of the fact thathydrogen is used to control M_(w) (or melt index) in olefinpolymerization, i.e. hydrogen is very effective in terminatingpropagating macromolecules and reducing the molecular weight of anethylene interpolymer.

Table 11 summarizes SEC deconvolution results, i.e. dual reactor Example14 and Comparative 14 were deconvoluted into first and second ethyleneinterpolymers. Table 11 shows the weight average molecular weights(M_(w)) of the first ethylene interpolymers were similar for Example 14and Comparative 14, i.e. 249,902 M_(w) Example 14 and 275,490 M_(w)Comparative 14; this similarity in M_(w) resulted even though 3 ppm ofhydrogen was used to produce the former and no hydrogen was used toproduce the latter. In other words, given Table 11 data it was evidentthat the bridged metallocene catalyst formulation produced highermolecular weight ethylene interpolymers, relative to the unbridgedsingle site catalyst formulation, at constant polymerizationtemperature, ethylene conversion and hydrogen concentration.

Table 11 also shows the bridged metallocene catalyst formulationincorporated more α-olefin into the first ethylene interpolymer, i.e.27.8 BrF (C₆/1000C) Example 14, relative to the unbridged single sitecatalyst formulation, i.e. 22.9 BrF (C₆/1000C); note that thisdifference in branch frequency occurred even though much less α-olefinwas employed to produce the former relative to the latter, as shown inTable 10A. In other words, the bridged metallocene catalyst formulationis much more efficient at incorporating α-olefin into the propagatingmacromolecule, relative to the unbridged single site catalystformulation.

FIG. 8 compares the SEC determined molecular weight distribution ofExample 14 and Comparative 14, as well as the GPC-FTIR determinedbranching frequencies as a function of molecular weight. Example 14'sbranching distribution curve (BrF) shows a large difference in theα-olefin content of the first ethylene interpolymer, i.e. 27.8 C₆/1000C(a first ethylene interpolymer density of 0.8965 g/cc) and the secondethylene interpolymer, i.e. 0.924 C₆/1000C (0.9575 g/cc). This largedifference in interpolymer density, i.e. Δρ=0.0610 g/cc=(ρ²−ρ¹), whereρ² is the density of the second ethylene interpolymer and ρ¹ is thedensity of the first ethylene interpolymer, reflects the fact thatExample 14 was produced in parallel reactor mode as well as thedifferent catalyst used in reactors 1 and 2. Higher Δρ's areadvantageous in several end-use applications, one non-limiting exampleincludes higher film stiffness while maintaining or improving filmtoughness. In contrast, as shown in Table 11 the Δρ of Comparative 14was an order of magnitude lower, i.e. 0.0062 g/cc.

FIG. 9 illustrates the deconvolution of Example 4's experimentallymeasured SEC chromatogram into three components, i.e. a first ethyleneinterpolymer, a second ethylene interpolymer and a third ethyleneinterpolymer. Example 4 is characterized in Table 12. Example 4 wasproduced in the solution pilot plant (described above) employing thebridged metallocene catalyst formulation (CpF-2) where the volume of thethird reactor was 2.2 liters. To be more clear, as produced the ethyleneinterpolymer product Example 4 had the following overall values: an I₂of 0.87 dg/min, a density of 0.9112 g/cc and 105449 M_(w) (7.53M_(w)/M_(n)) as measured by SEC. As shown in FIG. 9 and Table 12,Example 4 contained: 37 wt % of a first ethylene interpolymer having aM_(w) of 230042 and a branch content of 16.3 C₆/1000C, 57 wt % of asecond ethylene interpolymer having a M_(w) of 22418 and a branchcontent of 21.3 C₆/1000C, and; 6 wt % of a third ethylene interpolymerhaving a M_(w) of 22418 and a branch content of 21.3 C₆/1000C (branchcontent was determined by deconvoluting GPC-FTIR data). The molecularweight distribution of the first, second and third ethyleneinterpolymers were characterized by Flory distributions, i.e.M_(w)/M_(n)=2.0. Table 12 discloses two additional samples, Examples 5and 6, also produced in the solution pilot plant employing the bridgedmetallocene catalyst formulation. The SEC and GPC-FTIR curves ofExamples 5 and 6 were also deconvoluted into a 1^(st), 2^(nd) and 3^(rd)ethylene interpolymer, as shown in Table 12.

Continuous Polymerization Unit (CPU)

Small scale continuous solution polymerizations were conducted on aContinuous Polymerization Unit, hereinafter CPU. These experimentscompare the performance of the bridged metallocene catalyst formulation(containing component A, CpF-1) with the unbridged single site catalystformulation (containing component C, PIC-1) in one reactor.

The single reactor of the CPU was a 71.5 mL continuously stirred CSTR,polymerizations were conducted at 160° C. and the reactor pressure wasabout 10.5 MPa. The CPU included a 20 mL upstream mixing chamber thatwas operated at a temperature that was 5° C. lower than the downstreampolymerization reactor. The upstream mixing chamber was used to pre-heatthe ethylene, optional α-olefin and a portion of the process solvent.Catalyst feeds and the remaining solvent were added directly to thepolymerization reactor as a continuous process. The total flow rate tothe polymerization reactor was held constant at 27 mL/minute. Thecomponents of the bridged metallocene catalyst formulation (component A,component M, component B and component P) were added directly to thepolymerization reactor to maintain the continuous polymerizationprocess. More specifically: component A and component B were premixed inxylene and injected directly into the reactor, and; component M andoptionally component P were premixed in process solvent and injecteddirectly into the reactor. In the comparative experiments, thecomponents of the unbridged single site catalyst formulation (componentC, component M, component B and component P) were added directly to thepolymerization reactor to maintain the continuous polymerizationprocess. More specifically: component C and component B were premixed inxylene and injected directly into the reactor, and; component M andoptionally component P were premixed in process solvent and injecteddirectly into the reactor. In the examples, the component A employed wasCpF-1 [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂]. In the comparatives, the component Cemployed was PIC-1 ([Cp[(t-Bu)₃PN]TiCl₂]). Components M, B and P weremethylaluminoxane (MMAO-07), trityl tetrakis(pentafluoro-phenyl)borate,and 2,6-di-tert-butyl-4-ethylphenol, respectively. Upon injection, thecatalyst was activated in situ (in the polymerization reactor) in thepresence of ethylene and optional α-olefin comonomer. Component M wasadded such that the mole ratio of ([M]/[A]) or ([M]/[C]) was about 80;component B was added such that the mole ratio of ([M]/[A]) or ([M]/[C])was about 1.0, and; component P was added such that the mole ratio of([P]/[M]) was about 0.4.

Ethylene was supplied to the reactor by a calibrated thermal mass flowmeter and was dissolved in the reaction solvent prior to thepolymerization reactor. Optional α-olefin (comonomer, i.e. 1-octene) waspremixed with ethylene before entering the polymerization reactor, the(1-octene)/(ethylene) weight ratio varied from 0 to about 6.0. Ethylenewas fed to the reactor such that the ethylene concentration in thereactor varied from about 7 to about 15 weight %; where weight % is theweight of ethylene divided by the total weight of the reactor contents.The internal reaction temperature was monitored by a thermocouple in thepolymerization medium and was controlled at the target set point to±0.5° C. Solvent, monomer, and comonomer streams were all purified bythe CPU systems prior to entering the reactor.

The ethylene conversion, Q^(CPU), i.e. the fraction of ethyleneconverted was determined by an online gas chromatograph (GC) andpolymerization activity, K_(p) ^(CPU), having dimensions of[L/(mmol·min)] was defined as:

$K_{p}^{CPU} = {Q^{CPU}\left( \frac{1 - Q^{CPU}}{\lbrack{catalyst}\rbrack \times {HU}T^{CPU}} \right)}$

where HUT^(CPU) was a reciprocal space velocity (Hold Up Time) in thepolymerization reactor having dimensions of minutes (min), and;[catalyst] was the concentration of catalyst in the polymerizationreactor expressed in mmol/L of titanium or hafnium. In CPU experiments,Q^(CPU) was held constant at about 90% and the HUT^(CPU) was heldconstant at about 2.5 minutes. Downstream of the reactor the pressurewas reduced to atmospheric pressure. The ethylene interpolymer productwas recovered as a slurry in the process solvent and subsequently driedby evaporation in a vacuum oven prior to characterization.

CPU conditions were adjusted to synthesize ethylene interpolymerproducts at approximately constant melt index and density; morespecifically, an ethylene interpolymer product was synthesized using thebridged metallocene catalyst formulation and a comparative ethyleneinterpolymer product was synthesized using the unbridged single sitecatalyst formulation. As shown by each row in Table 13, the ‘% ImprovedM_(w)’ was at least 10% when one compares the M_(w) ^(A) of the ethyleneinterpolymer product produced with the bridged metallocene catalystformulation and the M_(w) ^(C) of the comparative ethylene interpolymerproduct produced with the unbridged single site catalyst formulation.

As shown in Table 14, the reactor's (α-olefin/ethylene) weight ratio hadto be adjusted such that ethylene interpolymer products were produced attarget density. To be more clear, using the bridged metallocene catalystformulation an (α-olefin/ethylene)^(A) was required to synthesize anethylene interpolymer product at target density; and using the unbridgedsingle site catalyst formulation an (α-olefin/ethylene)^(C) was requiredto synthesize a comparative ethylene interpolymer product at targetdensity. As shown by each row in Table 14 the bridged metallocenecatalyst formulation allows the operation of the continuous solutionpolymerization process at an improved (reduced) (α-olefin/ethylene)weight ratio relative to the control unbridged single site catalystformulation, i.e. the % Reduced [α-olefin/ethylene] weight ratio was atleast −70%.

Ethylene interpolymer product Example 20 was also produced on the CPUdescribed above. Example 20 demonstrates the ability of the bridgedmetallocene catalyst formulation containing CpF-2((2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂) to produce a low density product that waselastomeric in nature, i.e. Example 20 was characterized as follows:0.8567 g/cc, 72.9 BrF C₆/1000C, 14.6 mole percent 1-octene and 40.6weight percent 1-octene.

Monolayer Films

Monolayer blown film samples of ethylene interpolymer product Examples 1and 2 and Comparatives 15 and 16 were prepared as disclosed in Table 15.Examples 1 and 2 have been described earlier; Comparatives 15 and 16were pilot plant samples produced by injecting the unbridged single sitecatalyst formulation (PIC-1) into R1 and R2 (series mode). Monolayerblown film was produced on a Gloucester extruder, 2.5 inch (6.45 cm)barrel diameter, 24/1 L/D (barrel Length/barrel Diameter) equipped with:a barrier screw; a low pressure 4 inch (10.16 cm) diameter die with a 35mil (0.089 cm) die gap, and; a Western Polymer Air ring. The extruderwas equipped with the following screen pack: 20/40/60/80/20 mesh. Blownfilm, of about 1.0 mil (25.4 pam) thick, was produced at a constantoutput rate of about 100 lb/hr (45.4 kg/hr) by adjusting extruder screwspeed, and; the frost line height (FLH) was maintained from 16 to 18inch (40.64 to 45.72 cm) by adjusting the cooling air. Additional blownfilm processing conditions are disclosed in Table 15.

Given Table 15, it is evident that the blown film extruder pressure ofExamples 1 and 2 were from −16% to −29% lower, relative to Comparatives15 and 16. Lower blown film extruder pressure was an advantage becausethe output (lb/hr) of a blown film line may be limited by extruderpressure. In addition, the extruder amps of Example 1 and 2 were from−10% to −26% lower, relative to Comparative 15 and 16. Lower blown filmextruder amps was an advantage because the electrical power consumptionof a blown film line can be reduced if the ethylene interpolymerproducts disclosed herein are use.

Monolayer film physical properties are disclosed in Table 16 along withselected physical properties of the Examples 1 and 2 and Comparatives 15and 16. An ethylene interpolymer product having high melt strength wasadvantageous in the blown film conversion process, i.e. blown filmoutput is frequently limited by blown film bubble instability and thebubble stability improves as resin melt strength increases. The meltstrengths (measured in centi-Newtons (cN)) of Examples 1 and 2 were from25% to 65% higher, relative to Comparatives 15 and 16. Flow activationenergies (kJ/mol) of Examples 1 and 2 were from 42% to 66% higher,relative to Comparatives 15 and 16. Higher flow activation energies aredesirable because such resins are more responsive to changes inextrusion temperature, e.g. given a higher flow activation energy resinviscosity decreases more rapidly (decreasing extruder pressure and amps)with a given increase in extrusion temperature.

Desirable film physical properties include film optical properties, e.g.low film haze and high film Gloss 45°. Optical properties are importantwhen a consumer purchases an item packaged in a polyethylene film.Elaborating, a package having better contact and/or see-through claritywill have lower internal film haze and higher film gloss or sparkle. Afilm's optical properties correlate with the consumer's perception ofproduct quality. Given Table 16, it was evident that the haze ofExamples 1 and 2 were −40% to −45% lower (improved), relative toComparatives and 16, and; film Gloss 45° of Examples 1 and 2 were 16% to21% higher (improved), relative to Comparatives 15 and 16. Additionalblown film physical properties are summarized in Table 16.

Multilayer Films

Multilayer films were produced on a 9-layer line commercially availablefrom Brampton Engineering (Brampton ON, Canada). The structure of the9-layer films produced is shown in Table 17. Layer 1 contained thesealant resin under test. More specifically, layer 1 contained 91.5 wt %of the sealant resin, 2.5 wt. % of an anti-block masterbatch, 3 wt. % ofa slip masterbatch and 3 wt. % of a processing aid masterbatch, suchthat layer 1 contained 6250 ppm of anti-block (silica (diatomaceousearth)), 1500 ppm of slip (eurcamide) and 1500 ppm of processing aid(fluoropolymer compound); additive masterbatch carrier resins wereLLDPE, about 2 melt index (I₂) and about 0.918 g/cc. Layer 1 was theinsider layer, i.e. inside the bubble as the multilayer film wasproduced on the blown film line. The total thickness of the 9 layer filmwas held constant at 3.5-mil; the thickness of layer 1 was 0.385 mil(9.8 μm), i.e. 11% of 3.5 mil (Table 17). Layers 1-4 and 6-8 containedSURPASS FPs016-C an ethylene/1-octene copolymer available from NOVAChemicals Corporation having a density of about 0.917 g/cc and a meltindex (I₂) of about 0.60 dg/min. Layers 4, 6 and 8 also contained 20 wt.% Bynel 41E710 a maleic anhydride grafted LLDPE available from DuPontPackaging & Industrial Polymers having a density of 0.912 g/cc and amelt index (I₂) of 2.7 dg/min. Layers 5 and 9 contained Ultramid C40 L anylon (polyamide 6/66) available from BASF Corporation having a meltindex (I₂) of 1.1 dg/min. The multilayer die technology consisted of apancake die, FLEX-STACK Co-extrusion die (SCD), with flow paths machinedonto both sides of a plate, the die tooling diameter was 6.3-inches, inthis disclosure a die gap of 85-mil was used consistently, film wasproduced at a Blow-Up-Ratio (BUR) of 2.5 and the output rate of the linewas held constant at 250 lb/hr. The specifications of the nine extrudersfollow: screws 1.5-in diameter, 30/1 length to diameter ratio,7-polyethylene screws with single flights and Madddox mixers, 2-Nylonscrews, extruders were air cooled, equipped with 20-H.P. motors and allextruders were equipped with gravimetric blenders. The nip andcollapsing frame included a Decatex horizontal oscillating haul-off andpearl cooling slats just below the nips. The line was equipped with aturret winder and oscillating slitter knives. Table 18 summarizes thetemperature settings used. All die temperatures were maintained at aconstant 480° F., i.e. layer sections, mandrel bottom, mandrel, innerlip and outer lip.

End users often desire improvements and/or a specific balance of severalfilm properties. Non-limiting examples include optical properties,melting point for a given density, heat seal and hot tack properties,and others. Elaborating, within the packaging industry there is a needto improve the heat seal and hot tack properties of films. For example,it is particularly desirable to lower the seal initiation temperature(SIT) and broaden the hot tack window while maintaining, or improving,other film physical properties such as stiffness, toughness and opticalproperties.

Table 19 discloses cold seal data and seal initiation temperatures (SIT)of four 9-layer films coded (i) through (iv). Layer 1 of film (i), thesealant layer, contained the following binary blend: 70 wt. % of Example1 and 30 wt. % of Comparative 5; the latter was SCLAIR FP120 (0.920 g/ccand 1.0 I₂); layer 1 also contained additives as described above. Layer1 of film (i) had a blended density of about 0.909 g/cc. Surprisingly,as shown in FIG. 10 , the cold seal curves of film (i) and Comparativefilm (ii) were essentially equivalent; surprising because film (ii)'slayer 1 was 0.906 g/cc. Further, as shown in Table 19, the SIT's offilms (i) and (ii) were essentially equivalent, i.e. 92.4 and 92.2° C.,respectively, again surprising given the difference in layer 1densities, i.e. 0.909 g/cc versus 0.906 g/cc, respectively. To be moreclear, the polyethylene film art is replete with examples disclosingthat seal initiation temperature (SIT) increases as film (i.e. thesealant layer) density increases; FIG. 10 evidences this trend, i.e. thecold seal curve of film (iv) having a layer 1 density of 0.914 g/cc wasshifted to higher temperatures resulting in an SIT of 102.5° C. SIT(Table 19).

FIG. 10 and Table 19 demonstrate at least two advantages of the ethyleneinterpolymer products disclosed herein, specifically: (a) at constantSIT, a film (or layer) having a higher density is desired (film (i))because the film is stiffer and more easily processed through packagingequipment, relative to a lower density comparative film, and; (b) theethylene interpolymer products disclosed herein can be diluted withhigher density LLDPE's, i.e. the overall cost of the sealant resinformulation can be reduced.

Specific hot tack properties are desired in high speed vertical andhorizontal form-fill-seal processes where a product (liquid, solid,paste, part, etc.) is loaded and sealed inside a pouch-like package. Forexample, the packaging industry requires sealant resins that have broadhot tack windows, i.e. such resins consistently produce leak-proofpackages as various parameters are changed on the packaging equipment.Further, it is desirable that the Hot Tack Onset temperature HTO (in °C.) occurs at the lowest possible temperature. Also desirable is hightemperature hot tack such that the seal strength remains sufficient atelevated temperatures. Poor hot tack properties frequently limitpackaging line product rate.

Table 20 discloses hot tack data, the Hot Tack Onset (HTO) temperatureas well as comments on the manner in which the 9-layer films failed.Surprisingly, the HTO temperatures of films (iii) and (ii) were similar,i.e. 86.3 and 86.8° C., respectively; surprising given the difference inlayer 1 densities, i.e. 0.913 and 0.906 g/cc respectively. This issurprising because the polyethylene film art discloses that the HTOtemperature of a film (or layer) increases as film (or layer) densityincreases. Hot tack curves for film (iii) comprising Example 5 and film(ii) comprising Comparative 15 are shown in FIG. 11 . Even though thedensity of Example 5 (film (iii)) was higher, the breadth of Example 5'shot tack window was similar to Comparative 15 (film (ii)).

TABLE 1 FTIR unsaturation in ethylene interpolymer products Examples1-6, relative to Comparatives and the Unsaturation Ratio UR. InternalSide Chain Term Total UR = Sample Unsat/100° C. Unsat/100° C. Unsat/100°C. Unsat/100° C. (SC^(u) − T^(u))/T^(u) Example 1 0.011 0.006 0.0080.025 −0.25 Example 2 0.011 0.006 0.007 0.024 −0.14 Example 3 0.0140.009 0.009 0.032 0.00 Example 4 0.025 0.018 0.019 0.062 −0.05 Example 50.026 0.018 0.020 0.064 −0.10 Example 6 0.027 0.017 0.020 0.064 −0.15Example 8 0.016 0.003 0.008 0.027 −0.63 Comp Q1 0.014 0.012 0.011 0.0370.091 Comp Q2 0.017 0.016 0.015 0.048 0.067 Comp Q3 0.015 0.013 0.0120.040 0.083 Comp Q4 0.013 0.011 0.010 0.034 0.100 Comp R^(a) 0.0133 ±0.0140 ± 0.0057 ± 0.0330 ± 1.349 ± 0.0055 0.0077 0.0010 0.0046 0.907Comp S^(b) 0.0056 ± 0.0034 ± 0.0028 ± 0.0118 ± 0.1833 ± 0.0024 0.00230.0015 0.0026 0.0550 Comp. 1^(c) 0.0209 ± 0.0031 ± 0.0056 ± 0.0296 ±−0.4374 ± 0.0037 0.0010 0.0006 0.0041 0.1698 Comp 2^(d) 0.0133 ± 0.00270.0053 ± 0.0213 ± −0.5000 ± 0.0023 0.0006 0.006 0.0032 0.1000 Comp T^(e)0.0029 ± 0.0031 ± 0.0091 ± 0.0152 ± −0.6600 ± 0.0024 0.0014 0.00370.0052 0.1306 Comp U 0.003 0.002 0.006 0.011 −0.667 Comp 3^(f) 0.0050 ±0.0045 ± 0.0333 ± 0.0428 ± −0.8548 ± 0.0008 0.0006 0.0107 0.0099 0.0427Comp 4^(g) 0.0071 ± 0.0043 ± 0.0320 ± 0.0434 ± −0.8633 ± 0.0008 0.00150.0068 0.0080 0.0470 Comp 5^(h) 0.0050 ± 0.0065 ± 0.0492 ± 0.0607 ±−0.8687 ± 0.0016 0.0015 0.0025 0.0034 0.0296 Comp V^(i) 0.0046 ± 0.0032± 0.0254 ± 0.0332 ± −0.8737 ± 0.0029 0.0015 0.0039 0.0044 0.0663^(a)Average of 7 samples of Comparative R (Affinity) ^(b)Average of 9samples of Comparative S (Enable) ^(c)Average of 61 samples ofComparative 1 ^(d)Average of 3 samples of Comparative 2 ^(e)Average of48 samples of Comparative T (Exceed) ^(f)Average of 4 samples ofComparative 3 ^(g)Average of 21 samples of Comparative 4 ^(h)Average of137 samples of Comparative 5 ^(i)Average of 25 samples of Comparative V(Elite)

TABLE 2 Molecular and rheological features of linear and LCB examplesdisplayed in FIG. 5 of this disclosure.   n_(c)   m_(b)   M_(e)   M_(w)$\frac{M_{z}}{M_{w}}$   cosδ_(a) _(M) _(ω) Sample ID mol % g/mol g/molg/mol — — Comp. V2a 2.8 15.2 1.28E+03 1.03E+05 2.39 0.20 Comp. V3 3.415.4 1.36E+03 8.78E+04 2.2 0.11 Comp. V4 3 15.3 1.31E+03 9.83E+04 2.130.20 Comp. U1 3.2 15.3 1.33E+03 9.44E+04 1.86 0.21 Comp. T2 3.2 15.11.27E+03 1.04E+05 1.63 0.02 Comp. Q1 5 16.1 1.58E+03 8.33E+04 1.7 0.24Comp. Q2 8 17.4 2.05E+03 9.41E+04 1.76 0.23 Comp. Q3 5 16.1 1.58E+036.82E+04 1.87 0.16 Comp.Q4 3.8 15.6 1.41E+03 8.12E+04 1.86 0.27 Comp. R14.7 16.0 1.54E+03 8.45E+04 1.64 0.22 Comp. R2 3.6 15.5 1.39E+03 7.93E+041.62 0.29 Comp. R3 4.1 15.7 1.45E+03 6.43E+04 1.65 0.14 Comp. S1 2.314.8 1.18E+03 9.38E+04 1.95 0.44 Comp. S2 1.4 14.5 1.09E+03 1.09E+052.06 0.60 Com. S3 0.9 14.3 1.05E+03 1.00E+05 2.24 0.54 Com. S4 2 14.71.15E+03 1.02E+05 2.18 0.49 Comp. 3a 3.3 15.4 1.35E+03 1.06E+05 2.050.26 Comp. 5a 2.6 15.1 1.27E+03 1.15E+05 2.99 0.09 Resin 34 0.2 14.19.88E+02 1.01E+05 3.41 0.16 Example 1 4.7 16.0 1.54E+03 9.15E+04 2.690.36 Example 2 4.2 15.8 1.47E+03 9.04E+04 2.44 0.30 Example 8 3.9 15.61.43E+03 8.96E+04 1.96 0.24 a* C* a C Δ_(int.) Z Sample ID — — — — — —Comp. V2a 0.4654 0.1364 0.5376 0.7884 0.0435 80.6 Comp. V3 0.4854 0.00000.4776 0.4142 0.0260 64.6 Comp. V4 0.4248 0.0000 0.4619 0.7964 0.051775.1 Comp. U1 0.1914 0.0000 0.6113 0.7096 0.0591 70.8 Comp. T2 0.00000.0000 0.0000 0.0000 0.0000 82.1 Comp. Q1 0.0531 0.0000 0.2439 0.89480.0648 52.8 Comp. Q2 0.1050 0.0000 0.3746 0.8268 0.0629 45.8 Comp. Q30.2001 0.0000 0.1060 0.8518 0.0501 43.2 Comp. Q4 0.1914 0.0000 0.19410.9709 0.0617 57.5 Comp. R1 0.0000 0.0000 0.2931 0.8266 0.0648 55.0Comp. R2 0.0000 0.0000 0.2127 0.9739 0.0711 57.2 Comp. R3 0.0099 0.00000.0798 0.8522 0.0573 44.3 Comp. S1 0.2692 0.0000 0.3061 1.1695 0.075579.8 Comp. S2 0.3643 0.0000 0.3416 1.2500 0.0785 99.8 Com. S3 0.49720.0267 0.5318 1.1950 0.0751 95.8 Com. S4 0.4681 0.0000 0.3302 1.17830.0701 88.9 Comp. 3a 0.3557 0.0000 0.6417 0.8665 0.0637 78.9 Sample IDa* C* a C Δ_(int.) Z Com. 5a 0.6051 0.4427 0.6240 0.5196 0.0054 90.5Resin 34 0.9574 0.5903 0.3703 0.7634 −0.0049 102.2 Example 1 0.48180.3091 0.2994 1.0801 0.0427 59.6 Example 2 0.4607 0.1689 0.3430 0.96860.0468 61.7 Example 8 0.2779 0.0000 0.1764 0.9229 0.0545 62.9

TABLE 3 Neutron Activation Analysis (NAA), catalyst residues in ethyleneinterpolymer product Examples 1-9, relative to Comparatives. Sample Hf(ppm) Ti (ppm) Example 1 1.76 n.d. Example 2 1.98 n.d. Example 3 2.20n.d. Example 4 1.71 n.d. Example 5 1.51 n.d. Example 6 1.38 n.d. Example8 0.58^(†) 0.17^(†) Comparative Q1 0.28 n.d. Comparative Q2 0.34 n.d.Comparative Q3 0.24 n.d. Comparative Q4 0.24 n.d. Comparative R^(a) n.d.0.33 ± 0.01 Comparative S^(b) n.d. 0.14 Comparative U^(e) n.d. 0.73Comparative V^(i) n.d.  1.5 ± 0.06 Comparative 1 ^(c) n.d. 0.30 ± 0.06Comparative 2^(d) 0.58 ± 0.07 0.17 ± 0.06 Comparative 3^(f) 0.52 ± 0.036.34 ± 2.98 Comparative 4^(g) n.d. 6.78 ± 1.26 Comparative 5^(h) n.d.7.14 ± 1.22 ^(a)Comparative R, averages of Affinity ^(b)Comparative S(Enable B120) ^(c) Comparative 1, Nova Chemicals database average^(d)Comparative 2, NOVA Chemicals database average ^(e)Comparative U(Elite AT 6202) ^(f)Comparative 3, NOVA Chemicals database average^(g)Comparative 4, NOVA Chemicals database average ^(h)Comparative 5,Nova Chemicals database average ^(i)Comparative V, average (Elite)^(†)Example 8, average of catalytic residues in representative productsmade in the solution pilot plant employing a bridged nnetallocenecatalyst formulation in the first reactor and an unbridged metallocenecatalyst formulation in the second reactor

TABLE 4A Continuous solution process parameters for Examples 1-3. SampleExample 1 Example 2 Example 3 Reactor Mode Series Series Single R1Catalyst^(a) CpF-2 CpF-2 CpF-2 R2 Catalyst CpF-2 CpF-2 — R1 catalyst(ppm) 0.85 1.02 1.47 R1 ([M^(b)]/[A]) mole ratio 50 50 31 R1([P^(c)]/[M]) mole ratio 0.4 0.4 0.4 R1 ([B^(d)]/[A]) mole ratio 1.2 1.21.2 R2 catalyst (ppm) 0.60 0.57 n/a R2 ([M]/[A]) mole ratio 31 31 n/a R2([P]/[M]) mole ratio 0.4 0.4 n/a R2 ([B]/[A]) mole ratio 1.2 1.2 n/a R3volume (L) 2.1 2.1 2.1 ES^(R1) (%) 38 38 100 ES^(R2) (%) 62 62 0 ES^(R3)(%) 0 0 0 R1 ethylene concentration (wt %) 9.9 10.8 14.3 R2 ethyleneconcentration (wt %) 12.6 12.3 n/a R3 ethylene concentration (wt %) 12.612.3 n/a ((1-octene)/(ethylene))^(R1) (wt. fraction) 0.30 0.37 0.410((1-octene)/(ethylene))^(R2) (wt. fraction) 0.46 0.37 n/a(1-octene/ethylene) (wt. fraction, total) 0.324 0.263 n/a Prod. Rate(kg/h) 72 70 56 ^(a)[(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂] ^(b)methylalunninoxane(MMAO-7) ^(c)2,6-di-tert-butyl-4-ethylphenol ^(d)trityltetrakis(pentafluoro-phenyl)borate

TABLE 4B Continuous solution process parameters for Examples 1-3. SampleExample 1 Example 2 Example 3 Reactor Mode Series Series Single R1 totalsolution rate (kg/h) 266 238 400 R2 total solution rate (kg/h) 284 312250 R3 solution rate (kg/h) 15 15 15 Total solution rate (kg/h)^(a) 550550 650 OS^(R1) (%) 74.8 71.3 100 OS^(R2) (%) 25.2 28.7 n/a OS^(R3) (%)0 0 n/a H₂ ^(R1 (ppm)) 2.75 2.75 5.5 H₂ ^(R2 (ppm)) 16.0 12.0 n/a H₂^(R3 (ppm)) 0 0 n/a R1 feed inlet temp (° C.) 30 30 30 R2 feed inlettemp (° C.) 30 30 n/a R3 feed inlet temp(° C.) 130 130 130 R1 catalystinlet temp (° C.) 21 25 30 R2 catalyst inlet temp (° C.) 36 39 n/a R1Mean temp (° C.) 140 150 185 R2 Mean temp (° C.) 180 180 n/a R3 exittemp (° C.) 182 183 201 Q^(R1) (%) 80 80 80 Q^(R2) (%) 80 80 n/a Q^(T)(%) n/a n/a n/a ^(a)Total solution rate (kg/h) = (R1 total solution rate(kg/h)) + (R2 total solution rate (kg/h))

TABLE 5A Characterization of ethylene interpolymer product, Examples1-6, 8, 14 and 15. Sample Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 8 Ex.14 Ex. 15 Density (g/cc) 0.9045 0.9069 0.9028 0.9112 0.9134 0.91740.9167 0.9327 0.9144 I₂ (dg/min) 0.93 1.1 0.91 0.87 0.89 0.86 1.16 1.110.86 S.Ex. 1.58 1.52 1.44 1.73 1.75 1.74 1.37 1.66 1.54 I₂₁/I₂ 57 43.531.1 106 111 106 32.6 127 42.4 M_(w) 91509 90425 84299 105449 99451105774 89630 93038 80547 M_(w)/M_(n) 3.32 2.51 1.87 7.53 6.49 7.39 3.108.73 2.21 M_(z)/M_(w) 2.69 2.44 1.63 4.12 3.44 4.74 1.96 3.36 1.90 BrFC₆/1000° C. 23.4 20.9 22.3 18.1 15.5 14.1 17.9 13.5 16.0 Mol % 4.7 4.24.5 4.4 4.1 3.7 3.6 2.7 3.2 α-olefin¹ CDBI₅₀ 89.3 92.4 92.5 75.2 74.774.1 55.1 n/a 89.9 FAE (kJ/mol) 48.34 54.38 59.03 44.30 44.51 45.98 45.7n/a n/a MS (cN) 4.56 3.82 3.89 4.63 4.63 4.76 3.20 n/a 4.33 τ (s⁻¹)0.245 0.387 0.705 0.127 0.116 0.083 0.838 1.26 n/a ¹the mole fraction ofcomonomer, n_(c), was equivalent to ((Mol % α-olefin)/100).

TABLE 5B Characterization of comparative ethylene interpolymer products,Comparative 1a-5a and 14-16. Sample Comp 1a Comp 2a Comp 3a Comp 4a Comp5a Comp 14 Comp 15 Comp 16 Density (g/cc) 0.9162 0.9172 0.917 0.91240.9188 0.9059 0.9064 0.9064 I₂ (dg/min) 0.99 1.06 0.7 0.92 0.96 0.890.97 0.94 S.Ex. 1.27 1.45 1.4 1.24 1.34 1.66 1.24 1.42 I₂₁/I₂ 30.8 41.934.8 23.3 32.4 90.8 26 44.3 M_(w) 102603 96238 106261 107517 110365113541 107600 113161 M_(w)/M_(n) 3.08 2.65 2.99 2.51 3.65 5.52 2.96 3.42M_(z)/M_(w) 2.32 2.14 2.05 2.14 3.16 3.55 2.30 2.93 BrF C₆/1000° C. 14.615.8 16.7 18.1 12.9 23.4 21.2 21.2 Mol % 2.9 3.2 3.3 3.6 2.7 4.7 4.2 4.2α-olefin CDBI₅₀ 77.5 6.6 49.8 59.7 56.1 84.7 81.8 90.6 FAE (J/mol) 32.85n/a n/a 32.46 30.46 n/a 32.85 33.93 MS (cN) 2.78 3.29 5.26 7.7 6.46 n/a6.7 6.9 τ (s⁻¹) 12.9 n/a 0.467 8.37 3.09 n/a 12.9 3.27

TABLE 5C Characterization of comparative ethylene interpolymer products,Comparative Q1-Q4, R1-V1. Comp Comp Comp Comp Sample Q1 Q2 Q3 Q4 Density(g/cc) 0.9006 0.8827 0.9013 0.9093 I₂ (dg/min) 1.12 1.13 3.04 1.14 S.Ex.1.45 1.47 1.4 1.48 I₂₁/I₂ 33.4 37.5 31.4 36.1 M_(w) 83303 93355 6862882272 M_(w)/M_(n) 2 1.93 2.13 2.16 M_(z)/M_(w) 1.71 1.7 1.77 1.82 BrFC₆/1000° C. 24.3 38.5 24.6 18.6 Mol % 4.9 7.7 4.9 3.7 α-olefin CDBI₅₀92.1 97.6 89.4 86.7 FAE (J/mol) 57.12 54.68 50.67 60.64 MS (cN) 3.643.69 1.75 3.71 τ (s⁻¹) 0.745 0.714 6.89 0.565 Comp Comp Comp Comp CompSample R1 S1 T1 U1 V1 Density (g/cc) 0.9012 0.9205 0.9187 0.9081 0.9179I₂ (dg/min) 1.03 0.52 0.94 0.86 1.02 S.Ex. 1.41 1.56 1.11 1.34 1.33I₂₁/I₂ 30 39.6 15.8 30 30.2 M_(w) 83474 93531 110641 94385 98469M_(w)/M_(n) 1.79 2.74 2.18 2.18 2.74 M_(z)/M_(w) 1.63 1.91 1.71 1.862.17 BrF C₆/1000° C. 23.3 10.9 13.4 16.1 14.2 Mol % 4.7 2.2 2.7 3.2 2.8α-olefin CDBI₅₀ 89.2 88 70.8 86.5 57.1 FAE (J/mol) 56.60 56.82 29.59 n/a39.50 MS (cN) n/a n/a 2.04 n/a 7.06 τ (s⁻¹) 0.340 0.020 42.5 n/a 1.10

TABLE 6A Continuous solution process parameters for Example 6 andComparative 8, at about 1 I₂ and 0.9175 g/cc. Sample Example 6Comparative 8 Reactor Mode Series Series R1 Catalyst (i) CpF-2 PIC-1 R2Catalyst (ii) CpF-2 PIC-1 Density (g/cc) 0.9180 0.9170 Melt Index, I₂(dg/min) 0.92 1.00 Stress Exponent, S. Ex. 1.75 1.29 MFR, I₂₁/I₂ 10731.3 Branch Freq. (C₆/1000° C.) 18.3 14.4 R1 Catalyst, (i) (ppm) 0.360.10 R1 ([M]/[(i)]) (mole ratio) 31 100 R1 ([P]/[M]) (mole ratio) 0.400.30 R1 ([B]/[(i)]) (mole ratio) 1.20 1.20 R2 Catalyst, (ii) (ppm) 0.760.22 R2 ([M]/[(ii)]) (mole ratio) 31 25 R2 ([P]/[M]) (mole ratio) 0.40.30 R2 ([B]/(ii)]) (mole ratio) 1.2 1.30 ES^(R1) (%) 45 50 ES^(R2) (%)55 50 ES^(R3) (%) 0 0 R1 ethylene concentration (wt. fr.) 10.5 9.8 R2ethylene concentration (wt. fr.) 13.8 12.6 R3 ethylene concentration(wt. fr.) 13.8 12.6 ((1-octene)/(ethylene))^(R1) (wt. fr.) 0.19 1.40((1-octene)/(ethylene))^(R2) (wt. fr.) 0.30 0.0 ((1-octene)/(ethylene))Overall(wt. fr.) 0.25 0.71 OS^(R1) (%) 33.5 100 OS^(R2) (%) 66.5 0OS^(R3) (%) 0.0 0 H₂ ^(R1) (ppm) 2.75 0.4 H₂ ^(R2) (ppm) 10.0 0.8 H₂^(R3) (ppm) 0.0 0.0 Prod. Rate (kg/h) 93.0 81.3

TABLE 6B Continuous solution process parameters for Example 6 andComparative 8, at about 1 I₂ and 0.9175 g/cc. Sample Example 6Comparative 8 Reactor Mode Series Series R1 Catalyst (i) CpF-2 PIC-1 R2Catalyst (ii) CpF-2 PIC-1 Density (g/cc) 0.9180 0.9170 Melt Index, I₂(dg/min) 0.92 1.00 Stress Exponent, S.Ex. 1.75 1.29 MFR, I₂₁/I₂ 107 31.3Branch Freq. (C₆/1000° C.) 18.3 14.4 R3 volume (L) 2.2 2.2 R1 totalsolution rate (kg/h) 354.0 387.2 R2 total solution rate (kg/h) 246.0212.8 R3 solution rate (kg/h) 0.0 0 Total solution rate (kg/h) 600.0600.0 R1 inlet temp (° C.) 35 30 R1 catalyst inlet temp (° C.) 27.7 30.3R1 Mean temp (° C.) 148.2 140.1 R2 inlet temp (° C.) 45 30 R2 catalystinlet temp (° C.) 27.9 30.6 R2 Mean temp (° C.) 209.0 189.1 R3 exit temp(° C.) 210.2 191.6 Q^(R1) (%) 80.3 81.6 Q^(R2) (%) 85.0 83.9 Q^(R3) (%)70.3 53.6 Q^(T) (%) 97.1 95.6 Prod. Rate (kg/h) 93.0 81.3

TABLE 7A Continuous solution process parameters for Example 5 andComparative 9, at about 0.812 and 0.9145 g/cc. Sample Example 5Comparative 9 Reactor Mode Series Series R1 Catalyst (i) CpF-2 PIC-1 R2Catalyst (ii) CpF-2 PIC-1 Density (g/cc) 0.9153 0.9142 Melt Index, I₂(dg/min) 0.84 0.86 Stress Exponent, S. Ex. 1.76 1.32 MFR, I₂₁/I₂ 11435.7 Branch Freq. (C₆/1000° C.) 20.5 16.8 R1 Catalyst, (i) (ppm) 0.40.11 R1 ([M]/[(i)]) (mole ratio) 31 100 R1 ([P]/[M]) (mole ratio) 1.200.30 R1 ([B]/[(i)]) (mole ratio) 31.8 1.20 R2 Catalyst, (ii) (ppm) 0.780.14 R2 ([M]/[(ii)]) (mole ratio) 31 35 R2 ([P]/[M]) (mole ratio) 0.400.30 R2 ([B]/[ii]) (mole ratio) 1.20 1.50 ES^(R1) (%) 45 48 ES^(R2) (%)55 37 ES^(R3) (%) 0 15 R1 ethylene concentration (wt. fr.) 10.2 8.5 R2ethylene concentration (wt. fr.) 13.7 10.8 R3 ethylene concentration(wt. fr.) 13.7 12.0 ((1-octene)/(ethylene))^(R1) (wt. fr.) 0.2 1.72((1-octene)/(ethylene))^(R2) (wt. fr.) 0.34 0.00 ((1-octene)/(ethylene))Overall 0.277 0.826 (wt. fr.) OS^(R1) (%) 32 100 OS^(R2) (%) 68 0OS^(R3) (%) 0 0 H₂ ^(R1) (ppm) 2.75 0.4 H₂ ^(R2) (ppm) 10 0.8 H₂ ^(R3)(ppm) 0 0 Prod. Rate (kg/h) 93.9 79.4

TABLE 7B Continuous solution process parameters for Example 5 andComparative 9, at about 0.8 I₂ and 0.9145 g/cc. Sample Example 5Comparative 9 Reactor Mode Series Series R1 Catalyst (i) CpF-2 PIC-1 R2Catalyst (ii) CpF-2 PIC-1 Density (g/cc) 0.9153 0.9142 Melt Index, I₂(dg/min) 0.84 0.86 Stress Exponent, S.Ex. 1.76 1.32 MFR, I₂₁/I₂ 114 35.7Branch Freq. (C₆/1000° C.) 20.5 16.8 R3 volume (L) 2.2 2.2 R1 totalsolution rate (kg/h) 364 410 R2 total solution rate (kg/h) 236 160 R3solution rate (kg/h) 0 30 Total solution rate (kg/h) 600 600 R1 inlettemp (° C.) 35 35 R1 catalyst inlet temp (° C.) 27.7 30.3 R1 Mean temp(° C.) 146 130 R2 inlet temp (° C.) 45 55 R2 catalyst inlet temp (° C.)27.9 30.6 R2 Mean temp (° C.) 209 177 R3 exit temp (° C.) 210 198.5Q^(R1) (%) 80 81 Q^(R2) (%) 85 87.9 Q^(R3) (%) 70.2 78 Q^(T) (%) 97.1 95Prod. Rate (kg/h) 93.9 79.4

TABLE 8 Comparison of bridged metallocene and unbridged single sitecatalyst formulations in a single reactor continuous solutionpolymerization process at 165° C., Examples 10-11 and Comparatives10s-11s, respectively. Sample Example 10 Comparative 10s Example 11Comparative 11s Reactor Mode Single Single Single Single R1 Catalyst^(a)CpF-2 PIC-1 CpF-2 PIC-1 α-olefin 1-octene 1-octene 1-octene 1-octene R1Mean temp (° C.) 165.0 165.4 165.0 165.1 H₂ ^(R1) (ppm) 4 4 6 6((1-octene)/(ethylene))^(R1) 0.17 ^(b) 1.05 ^(c) 0.30 ^(b) 1.10 ^(c)(wt. fraction) Q^(T) (%) 90.0 90.1 85.0 85.2 SEC M_(n) 43,397 23,23842,776 14,285 SEC M_(w) 82720 ^(d) 47,655 ^(e) 86,239 ^(d) 28,838 ^(e)SEC M_(z) 133,489 72,326 142,459 43,496 SEC M_(w)/M_(n) 1.91 2.05 2.022.02 BrF (#C₆/1000° C.) 15.9 16.1 21.6 21.4 % Reduced −83.8 −72.7[α-olefin/ethylene] ^(f) % Improved Mw ^(g) 73.6 199 ^(a)CpF-2 =[(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂]; PIC-1 = [Cp[(t-Bu)₃PN]TiCl₂] ^(b)(α-olefin/ethylene)^(A), bridged single site catalyst formulation ^(c)(α-olefin/ethylene)^(C), unbridged single site catalyst formulation ^(d)M_(w) ^(A), bridged metallocene catalyst formulation ^(e) M_(w) ^(C),unbridged single site catalyst formulation ^(f) % Reduced(α-olefin/ethylene) = 100 × (((α-olefin/ethylene)^(A) −(α-olefin/ethylene)^(C))/(α-olefin/ethylene)^(C)) ^(g) % Improved M_(w)= 100 × ((M_(w) ^(A) − M_(w) ^(C))/M_(w) ^(C))

TABLE 9 Comparison of bridged metallocene and unbridged single sitecatalyst formulations in a single reactor continuous solutionpolymerization process at 190° C. and at 143° C., Examples 12-13 andComparatives 12s-13s, respectively Sample Example 12 Comparative 12sExample 13 Comparative 13s Reactor Mode Single Single Single Single R1Catalyst^(a) CpF-2 PIC-1 CpF-2 PIC-1 (component A, or component C)α-olefin 1-octene 1-octene 1-octene 1-octene R1 Mean temp (° C.) 190.0190.1 143.0 143.0 H₂ ^(R1) (ppm) 2 2 18 18 ((1-octene)/(ethylene))^(R1)0.17 ^(b) 1.85 ^(c) 0.05 ^(b) 0.45 ^(c) (wt. fraction) Q^(T) (%) 85.085.2 80.0 80.2 SEC M_(n) 40618 23106 44718 13612 SEC M_(w) 79790 ^(d)46836 ^(e) 77190 ^(d) 27341 ^(e) SEC M_(z) 129396 70817 115557 41142 SECM_(w)/M_(n) 1.96 2.03 1.73 2.01 BrF (#C₆/1000° C.) 13.0 13.0 4.8 4.5 %Reduced −90.8 −88.9 [α-olefin/ethylene] ^(f) % Improved Mw ^(g) 70.4 182^(a)CpF-2 = [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂]; PIC-1 = [Cp[(t-Bu)₃PN]TiCl₂]^(b) (α-olefin/ethylene)^(A), bridged metallocene catalyst formulation^(c) (α-olefin/ethylene)^(C), unbridged single site catalyst formulation^(d) M_(w) ^(A), bridged metallocene catalyst formulation ^(e) M_(w)^(C), unbridged single site catalyst formulation ^(f) % Reduced(α-olefin/ethylene) = 100 × (((α-olefin/ethylene)^(A) −(α-olefin/ethylene)^(C))/(α-olefin/ethylene)^(C)) ^(g) % Improved M_(w)= 100 × ((M_(w) ^(A) − M_(w) ^(C))/M_(w) ^(C))

TABLE 10A Physical properties of dual reactor Example 14 and Comparative14 and solution process conditions in reactor 1 (R1) using the bridgedmetallocene catalyst formulation (Example 14) or the unbridged singlesite catalyst formulation (Comparative 14). Sample Example 14Comparative 14 Melt Index, I₂, dg/min 1.11 0.89 Density, g/cc 0.93270.9059 MFR, I₂₁/I₂ 127 90.6 BrF (C₆/1000° C.) 13.5 23.4 M_(w) 93038113541 M_(w)/M_(n) 8.73 5.25 Reactor Mode Parallel Series R1 CatalystCpF-2 PIC-1 R1 Catalyst (i) (ppm) 0.43 0.13 R1 ([M]/[(i)]) mole ratio 31122 R1 ([P]/[M]) mole ratio 0.40 0.40 R1 ([B])/[(i)]) mole ratio 1.201.47 ES^(R1) (%) 40 38 R1 ethylene concentration (wt. %) 7.8 7.3((1-octene)/(ethylene))^(R1) (wt. fraction) 0.35 2.76 % Reduced[α-olefin/ethylene] ^(a) −87.3 (1-octene)/(ethylene) (wt. fraction,total) 0.14 1.05 OS^(R1) (%) 100 100 H₂ ^(R1) (ppm) 3.0 0.0 R1 inlettemp (° C.) 30 30 R1 Mean temp (° C.) 118.1 119.3 Q^(R1) (%) 80.0 80.0^(a) % Reduced [α-olefin/ethylene] = 100 × ((0.35 − 2.76)/2.76)

TABLE 10B Dual reactor Example 14 and Comparative 14 solution processconditions in reactor 2 (R2) using the unbridged single site catalystformulation. Sample Example 14 Comparative 14 R2 Catalyst PIC-1 PIC-1 R2Catalyst (i) (ppm) 9.0 0.45 R2 ([M]/[(i)]) mole ratio 65 25 R2 ([P]/[M])mole ratio 0.3 0.30 R2 ([B]])/[(i)]) mole ratio 1.5 1.50 R3 volume (L)2.2 2.2 ES^(R2) (%) 60 62 ES^(R3) (%) 0 0 R2 ethylene concentration 12.610.8 (wt %) R3 ethylene concentration 10.1 10.8 (wt %)((1-octene)/(ethylene))^(R2) 0.0 0.0 (wt. fraction) OS^(R2) (%) 0 0OS^(R3) (%) 0 0 H₂ ^(R2) (ppm) 40.0 1.0 H₂ ^(R3) (ppm) 0.0 0.0 R1 totalsolution rate (kg/h) 249.0 309.2 R2 total solution rate (kg/h) 233.3240.8 R3 solution rate (kg/h) 0 0 Total solution rate (kg/h) 450.0 550.0R2 inlet temp (° C.) 50 30 R3 inlet temp(° C.) 131 130 R2 Mean temp (°C.) 199.9 175.5 R3 exit temp (actual) (° C.) 170.0 174.5 Q^(R2) (%) 9289.7 Q^(R3) (%) 4.7 12.4 Q^(T) (%) 93.7 93.7

TABLE 11 Deconvolution of dual reactor ethylene interpolymer productExample 14 into a first and a second ethylene interpolymer andcomparison with dual reactor Comparative 14. Below, EthyleneInterpolymer Product Properties (Overall) Sample Example 14 Comparative14 I₂ (CPA/Model) 1.11 0.89 Density 0.9327 0.9059 (CPA/Model) MFR,I₂₁/I₂ 127 90.6 BrF (C_(6/)1000° C.) 13.5 23.4 M_(w) 93038 113541M_(w)/M_(n) 8.73 5.25 Δ_(int.) 0.017 <0.01 Below, SEC Deconvolution IntoR1 and R2 Components SEC Deconvoluted SEC Deconvoluted EthyleneInterpolymers Ethylene Interpolymers 1^(st) 2^(nd) 1^(st) 2^(nd) WeightPercent (%) 40.7 59.3 30.9 69.1 M_(n) 126115 8678 137745 15352 M_(w)249802 15238 275490 30704 Polydispersity 2.0 2.0 2.0 2.0 M_(w)/M_(n) BrF(C₆/1000° C.) 27.8 0.924 22.9 22.7 I₂ 0.04 1445 0.016 81.70 Density(g/cc) 0.8965^(a) 0.9575^(b) 0.9016^(a) 0.9078^(b) ^(a)p¹ = (−a₁ − (a₁ ²− 4*a₀*(a₂ − (BrF(C6/1000° C.)))^(0.5)))/(2*a₀); where a₀ = 9341.81, a₁= −17765.91 and a₂ = 8446.849 bp² = (p^(f) − wt¹*p¹)/(wt²); where p¹, p²and p^(f) are the densities of the 1^(st) and 2^(nd) interpolymer andthe overall (blend) density, and wt¹ and wt² represent the respectiveweight fractions

TABLE 12 Deconvolution of ethylene interpolymer products Examples 4-6into a first, a second and a third ethylene interpolymer. Sample Example4 Example 5 Example 6 R3 vol. (L) 2.2 2.2 2.2 I₂ (dg/min) 0.87 0.89 0.86Density 0.9112 0.9134 0.9174 (g/cc) MFR, I₂₁/I₂ 105 110 106 M_(w) 10544999451 105774 M_(w)/M_(n) 7.53 6.49 7.39 BrF C₆/ 18.1 15.49 14.05 1000°C. CDBI₅₀ 75.2 74.7 74.1 UR −0.053 −0.100 −0.150 Below, SECDeconvolution Into R1, R2 and R3 Components SEC Deconvoluted SECDeconvoluted SEC Deconvoluted Ethylene Ethylene Ethylene InterpolymersInterpolymers Interpolymers 1^(st) 2^(nd) 3^(rd) 1^(st) 2^(nd) 3^(rd)1^(st) 2^(nd) 3^(rd) Wt.Frac. 0.37 0.57 0.06 0.38 0.58 0.04 0.37 0.570.06 M_(n) 115000 11209 11209 119880 10332 8762 114689 10629 8852 M_(w)230042 22418 22418 239761 20664 17524 229378 21259 17704 M_(w)/M_(n))2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 BrF 16.3 21.3 21.3 14.219.8 20.0 11.6 18.2 18.2 (C₆/1000° C.)

TABLE 13 Percent (%) improved SEC weight average molecular weight(M_(w)) when using the bridged metallocene catalyst formulation relativeto the unbridged single site catalyst formulation (CPU at 160° C.reactor temperature and about 90% ethylene conversion). BridgedMetallocene Unbridged Single Site Weight % 1- Catalyst FormulationCatalyst Formulation % Improved octene in ethylene M_(w) ^(A) M_(w) ^(c)M_(w) interpolymers Component A (see¹) Component C (see²) (see³) 0.1CpF-1 293273 PIC-1 248166 18 2.5 CpF-1 130734 PIC-1 91198 43 5.0 CpF-1109858 PIC-1 73513 49 7.5 CpF-1 99227 PIC-1 64804 53 10.0 CpF-1 92315PIC-1 59257 56 12.5 CpF-1 87287 PIC-1 55285 58 15.0 CpF-1 83382 PIC-152237 60 17.5 CpF-1 80217 PIC-1 49792 61 20.0 CpF-1 77573 PIC-1 47766 6222.5 CpF-1 75314 PIC-1 46048 64 25.0 CpF-1 73348 PIC-1 44564 65 27.5CpF-1 71614 PIC-1 43262 66 30.0 CpF-1 70067 PIC-1 42107 66 32.5 CpF-168673 PIC-1 41072 67 35.0 CpF-1 67408 PIC-1 40136 68 37.5 CpF-1 66251PIC-1 39284 69 40.0 CpF-1 65186 PIC-1 38504 69 42.5 CpF-1 64202 PIC-137784 70 45.0 CpF-1 63287 PIC-1 37119 70 ¹M_(w) ^(A) = 164540 ×(Octene^(wt %)) − 0.251; where (Octene^(wt %)) is the weight % of octenein the ethylene/1-octene interpolymer ²M_(w) ^(C) = 121267 ×(Octene^(wt %)) − 0.311 ³100% × (M_(w) ^(A) − M_(w) ^(C))/M_(w) ^(C)

TABLE 14 Percent (%) improvement (reduction) in (α-olefin/ethylene)weight ratio in the reactor feed when using the bridged metallocenecatalyst formulation relative to the unbridged single site catalystformulation (CPU at 160° C. reactor temperature and about 90% ethyleneconversion). Bridged Unbridged Weight Metallocene Single Site % %Catalyst Catalyst Reduced 1-octene in Formulation Formulation (α-olefin/ethylene Com- (α-olefin/ Com- (α-olefin/ ethylene) inter- ponentethylene)^(A) ponent ethylene)^(C) Ratio polymers A (see¹) C (see²)(see³) 0.0 CpF-1 0.00 PIC-1 0.00 n/a 2.5 CpF-1 0.0078 PIC-1 0.183 −96%5.0 CpF-1 0.031 PIC-1 0.407 −92% 7.5 CpF-1 0.066 PIC-1 0.653 −90% 10.0CpF-1 0.112 PIC-1 0.920 −88% 12.5 CpF-1 0.170 PIC-1 1.21 −86% 15.0 CpF-10.238 PIC-1 1.52 −84% 17.5 CpF-1 0.318 PIC-1 1.85 −83% 20.0 CpF-1 0.409PIC-1 2.20 −81% 22.5 CpF-1 0.512 PIC-1 2.57 −80% 25.0 CpF-1 0.625 PIC-12.97 −79% 27.5 CpF-1 0.750 PIC-1 3.39 −78% 30.0 CpF-1 0.886 PIC-1 3.82−77% 32.5 CpF-1 1.03 PIC-1 4.28 −76% 35.0 CpF-1 1.19 PIC-1 4.76 −75%37.5 CpF-1 1.36 PIC-1 5.26 −74% 40.0 CpF-1 1.54 PIC-1 5.78 −73% 42.5CpF-1 1.74 PIC-1 6.33 −73% 45.0 CpF-1 1.94 PIC-1 6.89 −72%¹(α-olefin/ethylene)^(A) = 0.0009 × (Octene^(wt %))² + 0.0027 ×(Octene^(wt %)) − 0.0046; where (Octene^(wt %)) is the weight % ofoctene in the ethylene/1-octene interpolymer ²(α-olefin/ethylene)^(C) =0.0017 × (Octene^(wt %))² + 0.0771 × (Octene^(wt %)) − 0.0208 ³100% ×((α-olefin/ethylene)¹ − (α-olefin/ethylene)^(C)/α-olefin/ethylene)^(C)

TABLE 15 Monolayer blown film conditions, Gloucester blown film line, 4inch die diameter and 35 mil die gap: Examples 1 and 2, relative toComparatives 15 and 16. Example Example Comparative Comparative Sample 12 15 16 Thickness (mil) 1 1 1 1 BUR 2.5:1 2.5:1 2.5:1 2.5:1 Film Layflat(in) 15.7 15.7 15.7 15.7 Melt Temp (° F.) 441 441 431 432 Output (lb/hr)99.8 99.6 100 100 FLH (in) 18 18 18 18 Magnehelic (in-H₂O) 13.0 11.010.8 10.3 Nip Pressure (psi) 30 30 30 30 Nip Speed: (ft/min) 129 129 13288 Current: (Amps) 27.8 28.7 37.7 32.1 Voltage: (Volts) 192 183 188 195Pressure (psi) 2882 2872 4040 3442 Screw Speed (rpm) 41 39 40 41

TABLE 16 Monolayer film physical properties: Examples 1 and 2, relativeto Comparatives 15 and 16. Sample Example Example ComparativeComparative 1 2 15 16 Density (g/cc) 0.905 0.907 0.906 0.906 I₂ (dg/min)0.93 1.12 0.97 0.94 Melt Flow 57.0 43.4 26 44.3 Ratio (I₂₁/I₂) S.Ex.1.58 1.52 1.24 1.42 Melt Strength (cN) 4.56 3.82 2.78 3.03 Flow Act.Energy 48.34 54.38 32.85 33.83 (kJ/mol) Onset shear 0.2454 0.3866 12.933.269 thinning (1/s) Film Haze (%) 3.8 4.0 6.7 6.9 Film Gloss at 45°75.2 74.5 64.0 62.0 Dart Impact (g/mil) 641 653 761 1100 Lub-TefPuncture 81 91 124 84 (J/mm²) MD Tear (g/mil) 137 161 201 214 TD Tear(g/mil) 270 292 330 304 MD 1% Sec 108.0 121.0 107.5 104.3 Mod. (Mpa) TD1% Sec 107.0 121.0 107.9 106.4 Mod. (Mpa) MD 2% Sec 100 113 99.3 97.7Mod. (Mpa) TD 2% Sec 99.0 111 99.1 99.3 Mod. (Mpa) MD Ten. Break 43.140.6 50.0 43.1 Str. (MPa) TD Ten. Break 38.8 40.8 41.8 38.8 Str. (MPa)MD Elong. at 481 493 516 481 Break (%) TD Elong. at 701 737 732 701Break (%) MD Ten. Yield 7.6 7.1 7.8 7.6 Str (MPa) TD Ten. Yield 7.5 7.07.7 7.5 Str (MPa) MD Elong at 10 10 10 10 Yield (%) TD Elong at 10 10 1010 Yield (%)

TABLE 17 The multilayer film structure (9-layers) used to prepare 3.5mil blown films, the material (sealant resin) under test was placed inlayer 1. % of Materials and Weight % in Each Layer Layer 9-layerMaterial A Material B Number structure Material wt. % Material wt. %Layer 9 11 C40 L 100 Layer 8 11 FPs016-C 80 Bynel 41E710 20 Layer 7 11FPs016-C 100 Layer 6 11 FPs016-C 80 Bynel 41E710 20 Layer 5 12 C40 L 100Layer 4 11 FPs016-C 80 Bynel 41E710 20 Layer 3 11 FPs016-C 100 Layer 211 FPs016-C 100 Layer 1 11 Test Material 91.5 Additive 8.5 Masterbatches

TABLE 18 Multilayer film fabrication conditions. All temperatures in °F. Barrel Barrel Barrel Barrel Extruder/ Feed zone zone zone zone LayerThroat 1 2 3 4 Screen Adaptor Layer 9 100 455 480 480 480 480 480(outside of bubble) Layer 8 75 360 420 410 410 410 410 Layer 7 75 360420 410 410 410 410 Layer 6 75 360 420 410 410 410 410 Layer 5 100 455480 480 480 480 480 Layer 4 75 360 420 410 410 410 410 Layer 3 75 360420 410 410 410 410 Layer 2 75 360 420 410 410 410 410 Layer 1 75 360420 410 410 410 410 (inside of Bubble)

TABLE 19 Cold seal data and SIT (Seal Initiation Temperature (° C.)) for9-layer films (i) through (iv). 9-Layer Film Code (i) (ii) (iii) (iv)Layer 1 Sealant Resin 70 wt % Example 1 + 30 wt % Comparative ExampleExample Comparative 5 15 5 15 Layer 1 Density (g/cc) 0.909^(a) 0.9060.913 0.914 Layer 1 I₂ (dg/min) Seal 0.95^(a) 0.97 0.89 0.86 Temp (° C.)Force (N) Force (N) Force (N) Force (N) 90 2.10 1.82 0.82 0.24 95 15.817.4 5.55 0.24 100 32.0 27.4 33.2 1.58 105 35.6 35.3 37.7 16.3 110 41.539.2 42.3 27.4 120 44.8 45.3 48.5 49.6 130 50.5 50.2 54.1 55.0 140 52.751.3 55.1 57.1 150 55.3 53.8 55.5 56.7 160 53.5 54.1 55.6 55.9 170 55.154.8 57.0 55.8 SIT @ 92.4 92.2 95.6 102.5 8.8N (° C.) Max. Force 55.354.8 57.0 57.1 (N) Temp. @ 150 170 170 140 Max Force ^(a) density ormelt index of the 70%/30% blend

TABLE 20 Hot tack data and HTO (Hot Tack Onset temperature (° C.)) for9-layer films (i) through liv). 9-Layer Film Code (i) (ii) (iii) (iv)Layer 1 70 wt. % Comparative Example Example Sealant Example 1 + 15 5 15Resin 30 wt % Comparative 5 Layer 1 0.909 0.906 0.913 0.914 Density(g/cc) Layer 1 I₂ 0.95 0.97 0.89 0.86 (dg/min) Hot Avg. Avg. Avg. Avg.Tack Force Failure Force Failure Force Failure Force Failure Temp (° C.)(N) Mode (N) Mode (N) Mode (N) Mode 80 0.29 no seal 0.20 no seal 0.24 noseal 0.23 no seal 85 0.31 no seal 0.69 no seal 0.52 no seal 0.24 no seal90 1.07 seal 1.54 seal 2.41 seal 0.20 no seal 95 1.95 seal 3.17 seal3.89 seal 0.29 no seal 100 3.22 seal 4.81 seal 5.16 seal 1.40 seal 1054.44 seal 5.37 seal 5.34 seal 3.91 seal 110 5.23 seal 7.52 seal 5.13seal 6.40 seal 115 6.20 seal 7.92 seal 6.14 seal 9.47 stretch 120 6.79stretch 8.26 seal 6.59 seal 9.21 stretch 125 10.05 stretch 11.85 s/p^(a) 8.37 seal 12.86 stretch 130 9.50 stretch 11.62 s/p 9.55 seal12.47 stretch 135 9.51 stretch 10.81 s/p 9.42 seal 9.56 stretch 140 9.27stretch 11.11 s/p 7.51 seal 9.12 stretch 145 6.65 stretch 9.20 s/p 7.74seal 7.92 stretch 150 6.75 stretch 8.16 s/p 6.62 seal 6.58 stretch 1555.39 stretch 7.12 s/p 5.28 seal 5.54 stretch 160 5.19 stretch 6.33 s/p4.49 seal 5.68 stretch 165 4.15 stretch 5.58 s/p 4.44 seal 5.49 stretch170 3.74 stretch 4.70 s/p 3.37 seal 3.50 stretch 175 2.86 stretch 4.05s/p 2.93 seal 3.27 stretch 180 2.87 stretch 3.44 s/p 2.68 stretch 2.33stretch Hot Tack 89.5 86.8 86.3 98.2 Onset (° C.) Max. 10.1 11.9 9.612.9 Force (N) Temp. @ 125 125 130 125 Max Force (N) ^(a)s/p =stretch/peel failure mode

We claim:
 1. A film comprising at least one layer comprising an ethyleneinterpolymer product comprising at least one ethylene interpolymer,wherein said ethylene interpolymer product is characterized by: a) anetwork parameter, Δ_(int.), defined by following inequalities,0.01 × (Z − 50)^(0.78) ≤ Δ_(int.) ≤ 0.1 × (Z − 60)^(0.78)0.01 ≤ Δ_(int) ≤ 0.07wherein Z is a normalized molecular weight defined by$Z = \frac{M_{w}}{M_{e}}$ wherein M_(w) is a weight average molecularweight of the said ethylene interpolymer product as measured usingconventional size exclusion chromatography and M_(e) is a molecularweight between entanglements of said ethylene interpolymer as defined by$M_{e} = {\frac{4}{5}\frac{\rho RTm_{b}^{3.49}}{24820}}$ wherein ρ isthe melt-state density having a value of 0.780 g/cm³ at absolutetemperature T having a value of 463.15 Kelvin, R is the gas constanthaving a value of 8.314 J/(mol·Kelvin), M_(b) is the molecular weightper backbone bond calculated in units of g/mol as follows:$m_{b} = \frac{{n_{c}M_{w/c}} + {28\left( {1 - n_{c}} \right)}}{2}$where n_(c) is the comonomer content in mole fraction determined byFourier transform infrared (FTIR) spectroscopy according to ASTMD6645-01 (2001) and M_(w/c) is the molecular weight of the comonomer;and b) a residual catalytic metal of from ≥0.03 to ≤5 ppm of hafnium,wherein said residual catalytic metal is measured using neutronactivation.
 2. The film of claim 1 comprising at least one layercomprising an ethylene interpolymer product having a dimensionlessunsaturation ratio, UR, of from ≥−0.40 to ≤0.06, where UR is defined bythe following relationship; UR = (SC^(U) − T^(U))/T^(U) wherein, SC^(U)is the amount of a side chain unsaturation per 100 carbons and T^(U) isamount of a terminal unsaturation per 100 carbons, in said ethyleneinterpolymer product, as determined by ASTM D3124-98 and ASTM D6248-98.3. The film of claim 1, wherein said ethylene interpolymer product issynthesized using a bridged metallocene catalyst formulation comprisinga component A defined by Formula (I)

wherein M is a metal selected from titanium, hafnium and zirconium; G isthe element carbon, silicon, germanium, tin or lead; X represents ahalogen atom, R₆ groups are independently selected from a hydrogen atom,a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryloxide radical, these radicals may be linear, branched or cyclic orfurther substituted with halogen atoms, C₁₋₁₀ alkyl radicals, C₁₋₁₀alkoxy radicals, C₆₋₁₀ aryl or aryloxy radicals; R₁ represents ahydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, aC₆₋₁₀ aryl oxide radical or alkylsilyl radicals containing at least onesilicon atom and C₃₋₃₀ carbon atoms; R₂ and R₃ are independentlyselected from a hydrogen atom, a C₁₋₂₀ hydrocarbyl radical, a C₁₋₂₀alkoxy radical, a C₆₋₁₀ aryl oxide radical or alkylsilyl radicalscontaining at least one silicon atom and C₃₋₃₀ carbon atoms, and; R₄ andR₅ are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical a C₆₋₁₀ aryl oxide radical, oralkylsilyl radicals containing at least one silicon atom and C₃₋₃₀carbon atoms.
 4. The film of claim 3, wherein said film is characterizedby one or more of the following: a) a film gloss at 45° that is from 10%to 30% higher relative to a comparative film of the same compositionexcept said ethylene interpolymer product is replaced with a comparativeethylene interpolymer product; b) a film haze that is from 30% to 50%lower compared to a comparative film of the same composition except saidethylene interpolymer product is replaced with said comparative ethyleneinterpolymer product; wherein, said comparative ethylene interpolymerproduct was manufactured by replacing said bridged metallocene catalystformulation used to manufacture said ethylene interpolymer product withan unbridged single site catalyst formulation; wherein said film glossat 45° is measured according to ASTM D2457-13 and said film haze ismeasured according to ASTM D1003-13.
 5. The film of claim 1, whereinsaid ethylene interpolymer product comprises a first ethyleneinterpolymer, a second ethylene interpolymer and optionally a thirdethylene interpolymer.
 6. The film of claim 1, wherein said ethyleneinterpolymer product has a melt index from 0.3 to 500 dg/minute and adensity from 0.855 to 0.975 g/cc; wherein melt index is measuredaccording to ASTM D1238 (2.16 kg load and 190° C.) and density ismeasured according to ASTM D792.
 7. The film of claim 1, wherein saidethylene interpolymer product further comprises from 0 to 25 molepercent of one or more α-olefins.
 8. The film of claim 7, wherein saidone or more α-olefins are C₃ to C₁₀ α-olefins.
 9. The film of claim 7,wherein said one or more α-olefins are 1-hexene, 1-octene or a mixtureof 1-hexene and 1-octene.
 10. The film of claim 1, wherein said ethyleneinterpolymer product has a polydispersity, M_(w)/M_(n), from 1.7 to 25,wherein the weight average molecular weight, Mw, and the number averagemolecular weight, M_(n), are measured using conventional size exclusionchromatography.
 11. The film of claim 1, wherein said ethyleneinterpolymer product has a CDBI₅₀ from 1% to 98%, wherein CDBI₅₀ ismeasured using CTREF.
 12. The film of claim 1, wherein said layerfurther comprises at least one second polymer.
 13. The film of claim 12,wherein said second polymer is one or more ethylene polymer, one or morepropylene polymer or a mixture of said ethylene polymers and saidpropylene polymers.
 14. The film of claim 1, wherein said film has athickness form 0.5 mil to 10 mil.
 15. The film of claim 1, wherein saidfilm comprises from 2 to 11 layers, wherein at least one layer comprisessaid ethylene interpolymer product.